Section No.  3.9
                                             Revision No.  0
                                             Date January 4, 1962
                                             Page 1 .of 10
                           Section 3.9

          METHOD 13B - DETERMINATION OF TOTAL FLUORIDE
                EMISSIONS FROM STATIONARY SOURCES
                 (Specific-Ion Electrode Method)
                             OUTLINE
                                                       Number of.
          Section                       Documentati on    Pages
SUMMARY                                     3.9            1
METHOD HIGHLIGHTS                         .3.9            8
METHOD DESCRIPTION
     1.   PROCUREMENT OF APPARATUS
          AND SUPPLIES                      3.9.1         20
     2.   CALIBRATION OF APPARATUS          3.9.2         25
     3.   PRESAMPLING OPERATIONS            3.9.3          6
     4.   ON-SITE MEASUREMENTS              3.9.4         21
     5.   POSTSAMPLING OPERATIONS           3.9.5         19
     6.   CALCULATIONS                      3.9.6          7
     7.   MAINTENANCE                       3.9.7          3
     8.   AUDITING PROCEDURES               3.9.8          7
     9.   RECOMMENDED STANDARDS FOR
          ESTABLISHING TRACEABILITY         3.9.9          1
    10.   REFERENCE METHOD                  3.9.10         2
    11.   REFERENCES                        3.9.11         1
    12.   DATA FORMS                        3.9.12        22

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                                             Section No. 3.9
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 2 of 10
                              SUMMARY

      In Method  13B,  total  fluorides  (gaseous and particulate)  are
 extracted  isokinetically  from  the  source  by using  a sampling
 train similar to  the one specified in  Method 5  (Section 3.4  of
 this  Handbook); however,  the  filter does not  have to be heated,
 and   it  may  be located  either  immediately  after the  probe  or
 between the  third  and fourth impingers.
,     The  specific-ion  electrode method  for  quantitatively  mea-
 suring  the  fluorides  collected in the  train is  applicable  to
 fluoride  (F) emissions from stationary sources, but not to  fluo-
 rocarbons  such as  Freon.   The concentration range of the method
 is  from  0.02 to 2,000  pg  F/ml;  <0.1 pg F/ml requires  extra  care.
 Sensitivity  of  the method  has  not been determined.
      An  interferent  in  the  collection of fluorides is grease on
 sample-exposed  surfaces.   The  fluoride absorption  into the grease
 causes low results due to a lack of sample recovery.  If it can
 be  shown to  the  satisfaction of the  administrator that samples
 contain only water soluble fluorides,  fusion and distillation may
 be  omitted from the analysis.

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                                             Section No. 3.9
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 3 of 10
                        METHOD HIGHLIGHTS

     Section  3.9  (Method  13B)  describes specifications  for the
sampling and analysis of total fluoride emissions from stationary
sources.   A  gas  sample   is  isokinetically  extracted from the
source  stream,  and  the fluorides in the  stream  are collected in
the sampling train.
     The sampling train is similar  to  that in EPA Method 5, with
a  few  exceptions—the  filter does not have to be  heated,  and it
may be  located  either  immediately after the probe or between the
third  and  fourth  impingers.   If it is between the  probe  and the
first  impinger,  a borosilicate  glass  or stainless  steel  filter
holder with a 20-mesh stainless steel screen filter support and a
silicone rubber gasket must  be used.   If it is between the third
and fourth  impingers,  a glass  frit filter support  may be used.
     Sampling is generally the same as in Method 5, but a nozzle
size that will  maintain  an isokinetic  sampling rate of <28 Ji/min
(<1.0  ft3/min)  must be used.  Samples and  standards  must  be the
same temperature  during analysis  by the  specific-ion electrode
(SIE).   A change of 1°C (2°F) will cause a 1.5% relative error in
the sample  measurements.   Lack  of  stability  in  the electrometer
can also  cause significant  error  in  the results, but  the main
cause  of  error has been found to  be  distillation during'sample
analyses.
     The collected  sample  is  recovered by  transferring the mea-
                                                                *.
sured condensate and impinger water to a sample container,  adding
the filter and the  rinsings  of all sample-exposed  surfaces to
this container,  and fusing and  distilling  the sample.  The dis-
tilled  sample is  then  analyzed with a SIE.  Fusion and distilla-
tion may be omitted if it can be shown to the satisfaction of the
administrator that  the samples  contain only  water soluble fluo-
rides .
     Collaborative tests have  shown that  fluoride concentrations
from 0.1 to  1.4 |jg  F/m3  could be determined with an intralabora-
tory precision  of 0.037  jjg F/m3 and an interlaboratory precision

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                                             Section No.  3.9
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 4 of 10

of 0.056 pg F/m3.   For these tests six contractors simultaneously
took duplicate  samples  from  a stack.   The collaborative test did
not find any bias in the analytical method.1
     The Method Description (Sections 3.9.1 to 3.9.9) is based on
the  detailed  specifications  in  the  Reference Method  (Section
3.9.10) promulgated by EPA on June 20, 1980.2
1.   Procurement of Apparatus and Supplies
     Section 3.9.1  gives  specifications,   criteria,  and  design
features for the  required  equipment and materials.  The sampling
apparatus for Method  13B has  the same design features as that of
Method  5,  except  for the  positioning of the  filter in the sam-
pling train.  This section can be used as a guide for procurement
and  initial  checks  of equipment  and  supplies.    The  activity
matrix  (Table 1.1)  at the  end of the section is a summary of the
details given in  the  text  and can be  used  as  a quick reference.
2.   Pretest Preparations
     Section 3.9.2  describes  the  required calibration procedures
for the Method  13B  sampling  equipment (same, as Method 5), except
for the  SIE.  A pretest checklist (Figure 3.1 or a similar form)
should  be  used to  summarize  the  calibration and other pertinent
pretest data.
     Section  3.9.3  describes  the  preparation  of  supplies  and
equipment needed  for  the sampling.   The pretest preparation form
(Figure 3.2  of  Section 3.4.3) can be. used as an equipment  check-
list.   Suggestions  for  packing the  equipment and  supplies  for
shipping are given  to help minimize breakage.
     Activity matrices  for the  calibration of equipment and the
presampling operations  (Tables 2.1 and 3.1)  summarize the activi-
ties detailed in the text.
3.   On-site Measurements
     Section  3.9.4  describes procedures  for sampling and  sample
recovery.   A  checklist (Figure  4.5) is  an easy  reference for
field personnel to  use  in  all sampling activities.

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                                             Section No. 3.9
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 5 of 10

4.   Posttest Operations
     Section  3.9.5  describes  the postsampling  activities  for
checking the  equipment  and the analytical procedures.  A form is
given  for  recording  data from the posttest equipment calibration
checks;  a  copy  of the  form  should  be included  in  the emission
test  final report.  A control  sample  of known (F) concentration
should  be   analyzed  before  analyzing  the  sample for  a quality
control  check on  the  analytical procedures.  The  detailed ana-
lytical procedures can  be removed for use  as  easy references in
the  laboratory.    An activity matrix (Table 5.1)  summarizes the
postsampling operations.
     Section  3.9.6  describes  calculations,  nomenclature,  and
significant digits for  the  data  reduction.  A programmed calcu-
lator is recommended to reduce calculation errors.
     Section 3.9.7 recommends routine  and preventive maintenance
programs.   The  programs are  not  required,  but their  use should
reduce equipment downtime.
5.   Auditing Procedures
     Section  3.9.8  describes  performance  and  system  audits.
Performance audits for  both the  analytical  phase  and the data
processing  are  described.   A checklist  (Figure  8.2)  outlines  a
system audit.
     Section  3.9.9  lists  the primary   standards  to  which the
working standards  or calibration  standards  should be traceable.
6.   References
     Section  3.9.10  contains  the promulgated Reference Method;
Section  3.9.11  contains  the  references used  throughout  this
text;  and  Section 3.9.12  contains  copies  of data  forms recom-
mended for Method  13B.

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                                             Section No.  3.9
                                             Revision No.  0
                                             Date January 4, 1982
                                             Page 6 of 10
                     PRETEST SAMPLING CHECKS
                    (Method 13B, Figure 3.1)

Date	  Calibrated by

Meter box number                AH@      	
Dry Gas Meter*

Pretest calibration factor Y 	|	 (within ±2% of the
  average factor for each calibration run).

Impinger Thermometer

Was a pretest temperature correction used?    _. _._    yes  	 no
  If yes, temperature correction   	  (within ±1°C (2°F)
  of reference values for calibration and within ±2°C (4°F) of
  reference values for calibration check)

Dry Gas Meter Thermometers

Was a pretest temperature correction made?  __]	 yes  	.no
  If yes, temperature correction 	 (within ±3°C (5.4°F) of
  reference value for calibration and within  6°C (10.8°F) of
  reference values for calibration check)

Stack Temperature Sensor*

Was a stack temperature sensor calibrated against a reference
  thermometer?  	 yes  	,___ no
  If yes, give temperature range with which the readings agreed
  within ±1.5% of the reference values 	 to 	K (°R)

Barometer

Was the pretest field barometer reading correct?  	 yes  	 no
  (within ±2.5 nun (0.1 in.) Hg of the mercury-in-glass barometer)

Nozzle*

Was the nozzle calibrated to the nearest 0.025 mm (0.001 in.)?
  	 yes  	 no
*Most significant items/parameters to be checked.

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                                           Section No. 3.9
                                           Revision No. 0
                                           Date January 4, 1982
                                           Page 7 of 10
                       ON-SITE MEASUREMENTS
                     (Method  13B, Figure 4.5)
 Apparatus
 Probe  nozzle:   stainless  steel 	  glass
  Button-hook 	 elbow 	  size
  Clean?
Probe  liner:  borosilicate 	  quartz 	  other
   Clean?
  Heating  system*
  Checked?
Pitot  tube:  Type S	  other
  Properly attached to probe?*  	
  Modifications
  _Pitot tube coefficient	
Differential pressure gauge:two inclined manometers
  other 	^     sensitivity	
Filter holder:borosilicate glass             glass frit
  filter support 	  silicone gasket 	  other
  Clean?	"
Condenser:  number of impingers	
  Clean?
  Contents:  1st 	     2nd          3rd	4th
  Cooling system
  Proper connections?
  Modifications
Barometer:  mercury	aneroid	  other
Gas density determination:  temperature sensor type 	
  pressure gauge
  temperature sensor properly attached to probe?*  	

Procedure

Recent calibration:  pitot tubes* 	
  meter box* 	  thermometers/thermocouples1
Filters checked visually for irregularities?*  	
Filters properly labeled?*
Sampling site properly selected?
Nozzle size properly selected?*
Selection of sampling time?
All openings to sampling train plugged to prevent pretest con
  tamination?  	
Impingers properly assembled?  	   -••
Filter properly centered?
Pitot tube-lines checked for plugging or leaks?*

(continued)

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                                           Section No.  3.9
                                           Revision No.  0            /"""N
                                           Date January 4,  1982
                                           Page 8 of 10
Figure 4.5 (continued)
Meter box leveled?  	  Periodically?
Manometers zeroed?
AH@ from most recent calibration
Nomograph setup properly?
Care taken to avoid scraping nipple or stack wall?*
Effective seal around probe when in-stack?  	
Probe moved at proper time?
Nozzle and pitot tube parallel to stack wall at all times?*
  Filter changed during run?  	
  Any particulate lost?
Data forms complete and data properly recorded?*
Nomograph setting changed when stack temp changed significantly?

Velocity pressure and orifice pressure readings recorded
  accurately?*  	
Sampling performed at a rate less than 1.0 cfm 	
Posttest leak check performed?*  	 (mandatory)
Leakage rate 	 @ in. Hg	
  Orsat analysis  	 from stack          integrated         '    /"~*\
  Fyrite combustion analysis 	  sample location 	    V_x
  Bag system leakchecked?*  _i	
  If data forms cannot be copied, record:
    approximate stack temp 	  volume metered 	
    % isokinetic calculated at end of each run 	__
SAMPLE RECOVERY

Brushes:  nylon bristle 	  other
  Clean?
Wash bottles:  polyethylene or glass
  Clean?
Storage containers:  polyethylene 	  other
  Clean?                         Leakfree?
Graduated cylinder/or balance:  subdivisions <2 ml?*
  other
  Balance:  type
Probe allowed to cool sufficiently?	
Cap placed over nozzle tip to prevent loss of particulate?*
During sampling train disassembly, are all openings capped?
Clean-up area description:
  Clean?  	  Protected from wind?
Filters:  paper 	  type
                _
  Silica gel:  type (6 to 16 mesh)?  new?  _ used?
  Color?                           Condition?
Filter handling:  tweezers used?
  surgical gloves?	  other
  Any fluoride spilled?*  	
(continued)

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                                           Section No.  3.9
                                           Revision No. 0
                                           Date January 4, 1982
                                           Page 9 of 10
Figure 4.5 (continued)

Water distilled?  	
Stopcock grease:  acetone-insoluble?
  heat-stable silicone?  	~
Probe handling:  distilled water rinse
Fluoride recovery from:  probe nozzle
      other
  probe fitting
  front half of filter holder
Blank:  filter     	
 probe liner
distilled water
Any visible particles on filter holder inside probe?:*
All jars adequately labeled?  __
  Liquid level marked on jars?*
  Locked up?  	
Filter blank
   Sealed tightly?
*M6st significant items/parameters to be checked.

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                                             Section No. 3.9
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 10 of 10
                                                                o
                METHOD 13B CHECKLIST FOR AUDITORS
                    (Method 13B, Figure 8.2)
Yes
No
Comment
OPERATION
                              Presampling Preparation

                    1.   Knowledge of process conditions
                    2.   Calibration of equipment, before each
                         field test
                              On-Site Measurements

                    3.   Sample train assembly
                    4.   Pretest leak check
                    5.   Isokinetic sampling
                    6.   Posttest leak check
                    7.   Record process conditions during sample
                         collection
                    8.   Sample recovery and data integrity
                              Postsampling

                    9.   Accuracy and precision of control sample
                         analysis
                   10.   Recovery of samples for distillation
                   11.   Calibration checks
                   12.   Calculation procedure/check
                                                                O
General Comments:
                                                                      O

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                                             Section No. 3.9.1
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 1 of 20
                       METHOD DESCRIPTION

1.0  PROCUREMENT OF APPARATUS AND SUPPLIES
     A  schematic of  the sampling  train used  in Method  13B  is
shown  in  Figure 1.1.  The train  and  the sampling procedures are
similar to EPA Method 5; the procedures  and equipment for Methods
13A  and  13B are  identical.   Commercial models  of  the train are
available.   For  those who want to  build their own, construction
details are  in  APTD-0581;3  allowable modifications are described
herein.   The operating,  maintenance,  and calibration procedures
for the sampling train are in APTD-0576.4  Since correct usage is
important  in obtaining valid results,  all users are  advised  to
read this  document and  to  adopt its  procedures unless alterna-
tives are outlined herein.
     Specifications,  criteria,  and/or design  features  are given
in this  section to  aid  in  the selection of  equipment which as-
sures  collection of  good quality  data.  Procedures  and  limits
(where applicable) for acceptance checks are also given.
     During  procurement  of equipment  and supplies,  a log  (Figure
1.2) should  be  used to record the descriptive titles and identi-
fication numbers (if applicable) of the  equipment and the results
of the acceptance  checks;  a  blank copy  of the procurement log is
in Section  3.9.12 for the convenience  of the  Handbook user.  If
calibration  is  required for the  acceptance check,  a calibration
log should be used to record the data.   Table  1.1  at the  end of
this section summarizes  the  quality assurance activities for the
procurement  and acceptance of apparatus  and supplies.
1.1  Sampling Apparatus
1.1.1 Probe  Liner  - The sampling probe  should be constructed  of
borosilicate glass  (Pyrex) or  316 stainless  steel tubing with an
outside diameter  (OD) of about  16  mm  (0.625  in.);  it should  be
encased in  a stainless  steel'  sheath  with an OD of 25.4 mm (1.0
in. ).
(I It-'

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  1.9-Z.5 cm
 (0.75-1 in.)
1.9 cm(0.75 1n.)

     PITOT TUBE
TEMPERATURE
   SENSOR
7
            PROBE
                  ,   OPTIONAL
                  'FILTER HOLDER'
                  I   LOCATION   I
                        !^U!LJ  FILTER HOLDER
             PROBE
          TYPE S    C
        PITOT TUBE
                                                                             ^THERMOMETER
                                                                                    CHECK
                                                                                   -.VALVE
                        ORIFICE
                       MANOMETER
                                           DRY TEST
                                             METER
                         Figure  1.1.   Fluoride  sampling train.
                                                                                    VACUUM
                                                                                     LINE
                                                                                                      *u \j %j (/)
                                                                                                      a> ru n> CD
                                                                                                      *> rt < o
                                                                                                      fD (D (-•• f+
                                                                                                          tn H-
                                                                                                          H-O
                                                                                                            to
                                                                                                        VD
                                                                                                        00
                                                                                                        fO
 O
                            o
                                                                             o

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Item description
Quantity
Purchase

  order

 number
Vendor
                                                                 Date
Ordered
Received
Cost
Dispo-
sition
Comments
                                                   C0
                                                                                                               n>
                                                                                                                   ja en
                                                                                                                   n> o>
                                                                                                                 rt < o
                                                                                                                   0) H-

                                                                                                                   M-O


                                                                                                                   §d
                                                                                                                     CO
                                    Figure 1.2.   Example of a procurement log.
                                                                                                                vo
                                                                                                                oo

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                                             Section No.  3.9.1
                                             Revision No.  0
                                             Date January 4,  1982
                                             Page 4 of 20

     A heating system may be required to maintain the exit gas at
120° ±14°C  (248° ±25°F)  during  sampling.   Other temperatures may
be  specified  by  a  subpart of the regulations or  approved by the
administrator.  Since the probe outlet temperature is not usually
monitored  during sampling,  probes  constructed in  accordance to
APTD-0581s  and calibrated with procedures in APTD-05764  will be
acceptable.
     Upon  receiving  a new  probe,  visually check  for specifica-
tions  (i.e.,  the length and composition  ordered)  and for breaks
or cracks; leak check on a sampling train (Figure 1.1); and check
the nozzle-to-probe connection with a Viton-O-ring or with Teflon
ferrules for  glass liners  or stainless steel ferrules for stain-
less steel liners.
     The probe heating system should be checked as follows:
     1.   Connect the  probe by attaching the nozzle  to  the pump
inlet.
     2.   Connect the probe  heater  to the electrical source, and
turn it  on for  2 or  3 min; it should become warm  to the touch.
     3.   Start  the  pump,  and  adjust the  needle valve  until a
flow rate of about 0.02 m3/min (0.75 ft3/min) is achieved.
     4.   Be  sure that the  probe  remains warm to  the touch and
that the  heater maintains  the exit  gas  at  a minimum  of 100°C
(212°F); if  not,  repair, return  to the  supplier,  or reject the
probe.
1.1.2  Probe Nozzle - The probe nozzle  should be designed with a
sharp,  tapered  leading edge and should be  constructed of either
seamless 316  stainless  steel tubing or glass formed in a button-
hook or  elbow configuration.  The  tapered  angle  should  be £30°,
with the  taper  on  the outside  to  preserve  a  constant inside
diameter (ID).
     A range  of  nozzle  ID's [e.g.,  0.32 to 1.27 cm (0.125 to 0.5      {)
in.) in  increments  of 1.6  mm (0.0625 in.)]  should be available
for  isokinetic  sampling.    Larger  nozzle sizes may  be  required

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                                             Section No.  3.'9.1
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 5 of 20

for hi-vol sampling  trains  or for very low stack gas velocities.
Each nozzle should be  engraved with an identification number for
inventory and for calibration purposes.
     Upon receipt of the  nozzle from the manufacturer and before
each test, inspect it  for roundness and corrosion and for damage
(nicks, dents,  and burrs) to the tapered edge,  and  check the ID
with  a  micrometer.    (Calibration  procedures  are  in  Section
3.9.2.)  Slight variations from exact ID'S should be expected due
to machining tolerances.  Reshape,  return to supplier or reject.
1.1.3  Pitot Tube -  The pitot tube,  preferably of Type S design,
shown  in  Figure  1.1 should  meet the  requirements  of  Method  2
(Section 3.1.2).  Proper pitot-tube-sampling-nozzle configuration
for prevention  of aerodynamic  interference is  shown  in Figures
2.6 and 2.7 of Method 2 (Section 3.1.2).
     Visually inspect the vertical and horizontal tip alignments.
If the tube is purchased as an integral part of a probe assembly,
check  the  dimensional clearances using  Figures 2.6  and 2.7 of
Section 3.1.2.   Repair or  return any  pitot tube that  does not
meet specifications.
1.1.4   Differential Pressure Gauge - The  differential  pressure
gauge  should  be  an  inclined  manometer  or  the equivalent,  as
specified in  Method  2, Section 3.1.2.  Two gauges  are required.
One is used to monitor the stack velocity pressure,  and the other
to measure the orifice pressure differential.
     Initially,  check the gauges against a gauge-oil manometer at
a minimum  of  three points—0.64,  12.7, and 25.4 mm  (0.025,  0.5,
and 1.0  in.)  H20—to  see  if they read  within 5%  at each  test
point.  Repair  or return  to the supplier any gauge that does not
meet these requirements.
1.1.5  Filters  -  If  the  filter is  between the  third  and fourth
impingers, use  a  Whatman No. 1 (or  equivalent)  filter,  sized to
fit the filter  holder.   If  it is between the probe and the first
impinger,  use  any suitable medium  (e.g.,  paper  or  organic  mem-
brane ) as long  as the  filter can withstand prolonged exposure up

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                                             Section No.  3.9.1
                                             Revision No.  0             S~~\
                                             Date January 4,  1982        (   )
                                             Page 6 of 20               V^X

to 135°C (275°F) and has >_95% collection efficiency (£5% penetra-
tion) for 0.3-p dioctyl phthalate smoke particles.
     Conduct  the  filter efficiency  test  before beginning  the
sampling by  using  either  the ASTM  Standard Method  D2986-71  or
test  data   from  the   supplier's  quality  control program.   The
filter should have a low F blank value (<_0.015 mg F/cm2 of filter
area);' determine  the  average  values  of  at least  three  filters
from the lot  to be used for sampling.  Glass  fiber filters  gen-
erally have high and/or variable F blank values, and thus are not
acceptable.
1.1.6  Filter Holder - If the filter is located between the probe
and first impinger a borosilicate glass or stainless steel filter
holder  with  a 20 mesh stainless  steel mesh frit filter support
and a silicone rubber gasket is required by the Reference Method.         -^
If it  is between the third and  fourth impingers,  the tester may       (   )
use  borosilicate  glass  with  a  glass  frit filter  support and a
silicone rubber gasket.  Other  gasket materials  (e.g., Teflon or
Viton) may be used if approved by the  administrator.
     The  holder  design must  provide a  positive  seal  against
leakage from the outside or around the filter.  The holder should
be durable,  easy to load,  and leak  free  in normal applications.
Check  visually  before use.  If  immediately following the probe,
the filter should be positioned toward the flow.
1.1.7   Filter Heating System -  Any  heating system  may  be  used
which  is  capable of maintaining  the filter holder at 120° ±14°C
(248° ±25°F)  during sampling.   Other  temperatures  may be speci-
fied by a  subpart of the regulations  or  approved by the  admini-
strator.   The heating  element  should  be easily  replaceable  in
case  of malfunction  during  sampling.  A gauge  capable  of mea-
suring  within  3°C (5.4°F)  should be used to monitor the  tempera-
ture around the filter during sampling.
     Check  the  heating system   and  the   temperature monitoring
device before sampling.

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                                             Section No. 3.9.1
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 7 of 20

1.1.8  Condenser - Four impingers with leak-free, noncontaminated
ground-glass or  similar fittings should be connected in series.
The  first,  third,  and  fourth  impingers  must be  £  modified
Greenburg-Smith design that has a glass tube (instead of inserts)
with an  unconstricted 13-mm (0.5-in.) ID  extending  to  within 13
mm (0.5  in.) of  the flask bottom.  The second impinger must be a
Greenburg-Smith with the standard tip and plate.  Modifications—
for example, using flexible connections between impingers,  using
materials  other  than glass, or  using a flexible  vacuum hose to
connect  the  filter holder to the condenser—must  be approved by
the  administrator."  The  fourth  impinger  outlet connection  must
allow insertion  of a thermometer capable of measuring ±1°C (2°F)
of true value in the range of 0° to 25°C (32° to 77°F).
     Alternatively,  any  system  that  cools the gas stream  and
allows measurement of  the  condensed  water and the  water vapor
leaving  the  condenser,  each to  within 1 ml or  1  g,  may be  used
with approval from the administrator.
     Upon  receipt of  a standard Greenburg-Smith  impinger,  fill
the  inner  tube with water;  if the water  does  not drain through
the orifice  in 6 to 8 s or less, replace or enlarge the impinger
tip to prevent an excessive pressure drop in the sampling system.
Check  each  impinger  visually  for  damage—breaks,  cracks,  or
manufacturing flaws such as poorly shaped connections.
1.1.9  Metering  System  -  The metering system should consist of a
vacuum gauge,  a  vacuum pump,  thermometers  capable  of  measuring
±3°C  (5.4°F)  of  true value  in the range  of 0° to  90CC (32° to
194°F),  a  dry gas  meter  with  ±2%  accuracy at  the required sam-
pling  rate,  and  related equipment  shown   in Figure  1.1.  Other
metering  systems  capable  of  maintaining rates  within  10%  of
isokinetic  and  determining sample volumes  within  2% may be used
if approved  by the administrator.   Sampling trains with metering
systems  designed for rates higher  than  those  described in APTD-
0581s and  APTD-05764  may be used if the above specifications can
be met.

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                                             Section .No.  3.9.1
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 8 of 20

     When  the  metering  system  is  used  with  a  pitot tube,  the
system should permit  verification of an isokinetic sampling rate
with a nomograph or by calculation.
     Upon receipt or after construction of the equipment, perform
both positive and  negative  pressure leak checks before beginning
the  calibration procedure  (Section 3.9.2).   Adjust,  repair,  or
replace  the  malfunctioning item.   Reject  a dry  gas  meter if it
behaves  erratically  or  if  it  cannot be  adjusted.   Reject the
thermometer if unable to calibrate.
1.1.10   Barometer  - A  mercury,  aneroid,  or other barometer capa-
ble of measuring atmospheric pressure to within ±2.5 mm  (0.1 in.)
Hg is require'd.
     Check a  new barometer against a mercury-in-glass barometer
or the  equivalent.   In lieu of this, obtain the absolute barom-
etric pressure  from a nearby weather service station and adjust
it for the elevation  difference between the station and the sam-
pling point;  accordingly, either subtract 2.5 mm Hg/30 m (0.1 in.
Hg/100 ft)  from the  station  value for  an  elevation increase or
add the  same  for an elevation decrease.  If the barometer cannot
be adjusted to  agree  within 2.5 mm (0.1 in.) Hg of the reference
barometric pressure,   either  return  it to  the  manufacturer or
reject it.
1.1.11  Gas Density Determination Equipment  -  A temperature sen-
sor and  a  pressure  gauge (Method 2, Section 3.1.2) are required.
A gas analyzer (Me'thod 3, Section 3.2.2) may be required.
     The  temperature   sensor  should be  permanently  attached to
either  the probe  or  the  pitot  tube;  in  either case,   a fixed
configuration (Figure  1.1)  should be maintained.  Alternatively,
the sensor may be attached just before field use (Section 3.9.2).
1-2  Sample Recovery Apparatus
1.2.1   Probe Liner and Nozzle Brushes  - Nylon  bristle  brushes
with  stainless  steel  wire  handles  are  recommended.  The probe     (  J
brush  must  be   at  least  as  long  as  the  probe.   A separate,
smaller,  and  very flexible brush should be  used for the nozzle.

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                                             Section No. 3.9.1
                                             Revision No. 0
                                             Date January 4, 196.2
                           .,                 Page 9 of 20

     Visually  check  for  damage  upon receipt,  and replace  or
return to supplier if defective.
1.2.2  Wash Bottles - Two 500-ml wash bottles are recommended for
the probe  and  the glassware rinsings.  Glass or polyethylene are
acceptable.
1.2.3  Sample Storage Containers - Recommended are 500 ml or 1000
ml  chemically  resistant,  high-density polyethylene  bottles  for
storage of  samples.   The bottles must have leak proof screw caps
with leak proof, rubber-backed Teflon cap liners, or they must be
constructed  to preclude  leakage and to  resist  chemical attack;
wide-mouthed bottles are easiest to use.
     Prior to field use, inspect the cap seals and the bottle cap
seating  surfaces  for  chips,   cuts,   cracks,  and  manufacturing
deformities which would allow leakage.
1.2.4   Graduated Cylinder and/or Triple Beam Balance -  Either  a
250-ml  glass  (Class A)   graduated  cylinder  or  a  triple beam
balance may be .used to measure the water condensed in the imping-
ers during  sampling.  The graduated cylinder may also be used to
measure water initially placed in the first and second impingers.
In either case,  the  required accuracy is 1 ml or 1 g; therefore,
the cylinders must have subdivisions <2 ml, and the balance  should
be capable of weighing to the nearest 0.1 g.
1.2.5   Plastic  Storage  Containers   - Several  airtight  plastic
containers are needed for storage of silica gel.
1.2.6   Funnel  and Rubber Policeman -  A  funnel and .a  rubber  po-
liceman  are needed  to  transfer  the  used  silica  gel  from  the
impinger to  a  storage container unless  silica  gel  is weighed in
the  field  after  the  test.  A  Teflon  policeman is  helpful  for
recovery of the filter.   The funnel should be glass with a  100-mm
diameter and a 100-mm stem.
     Visually check on receipt,  and replace or return if damaged.
1.3  Distilling Apparatus
     The  fluoride distillation  setup  is shown  in  Figure 1.3.
1.3.1   Flasks  -  A long-necked,   round  bottom 1-liter  flask with
24/40 joint grindings is  needed for boiling the sample solution.

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                                 a
                                      Section No. 3.9.1
                                      Revision No.  0
                                      Date January  4,  1982
                                      Page 10 of 20
                      o
            CONNECTING TUBE
               12-rmID
                '24/40
  THERMOMETER
    TIP MUST
  EXTEND BELOW
THE  LIQUID

  WITH  10/30
      24/40

    1-liter
     FLASK
     BUNSEN.
     BURNER
                                               24/40
CONDENSER
                                             250 ml
                                           VOLUMETRIC
                                             FLASK
                                                                      O
 Figure 1.3.  Fluoride distillation  apparatus.
                                                                      O

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                           ^                 Section No. 3.9.1
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 11 of 20

Also,  a  250-ml volumetric  (Class  A)  flask is  needed to receive
the condensate.
1.3.2  Thermometer  - A  thermometer for checking  the temperature
of the sample in the boiling flask should read within ±1°C (±2°F)
of the true  value  in the range of 100° to 200°C (212° to 392°F).
Check it against a mercury-in-glass thermometer.
1.3.3  Adapter - An adapter should  have joint grindings (inner
and  outer  parts)  that  are  24/40  at the bottom and 10/30 at the
top  that will  hold a  thermometer,  and it  should  have  a 24/40
joint  grinding (inner  part) at the  end of the top sidearm that
joins the connector tube.
1.3.4  Connector Tube - A tube with a standard or  a medium wall
and  with  a  13-mm  (0.5  in.)  ID  is  needed  for connecting the
adapter to the condenser.
1.3.5-   Condenser - A coiled  integral  Graham  condenser  (joint
grinding 24/40) with a jacket length of 300 mm  (12 in.) is needed
for condensation of the distillate.
1.4  Miscellaneous Glassware
1.4.1  Beaker  - A  1500-ml glass beaker  (Class  A) with 5-ml sub-
divisions is needed to receive the filtered sample from container
No. 1 or No. 2.
1.4.2  Pipettes - Several volumetric  pipettes  (Class A)—includ-
ing  5,  10,  20,  25, 50 mi's—should be  available.   Record the
stock  numbers,  and visually check  for cracks, breaks,  or manu-
facturer's flaws.  If irregularities are found, either replace or
return to the supplier.
1.4.3  .Volumetric  Flasks -  The following  volumetric  flasks are
needed for performing  the  analysis:   a  50-ml  glass volumetric
flask  (Class A)  is  needed to dilute the sample aliquot to 50 ml
with TISAB (total ionic strength adjustment buffer)   in determina-
tion  of  fluoride  concentration;   a  l-£  glass  volumetric flask
(Class A)  to  dilute  the fused sample  to volume with distilled
water;  and  several 100-ml polyethylene  volumetric  flasks  to
prepare the fluoride standardizing solution.
                                                          I

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                                     }'     /   Section No.  3.9.1
                                             Revision No.  0
                                             Date January 4,  1982
                                             Page 12 of 20

1.5  Reagents and other Supplies (Sampling)
     Unless  otherwise indicated,  all  reagents  should meet the
specifications  of  the Committee  on Analytical  Reagents  of the
American Chemical  Society (ACS);  otherwise, use  the best avail-
able grade.
1.5.1  Silica Gel - Use indicating type 6-16 mesh.  If previously
used, dry  at  175°C  (347°F)  for at least 2 h before reusing.  New
silica gel may be used as received.
1.5.2  Water  -  Deionized distilled water  should  conform to  ASTM
specification D1193-74,  Type 3.  At the  option  of  the  analyst,
the  KMnO^  (potassium  permanganate)  test  for  oxidizable organic
matter may be omitted if high concentrations of organic matter
are not expected.
1.5.3   Crushed  Ice  -  Enough  crushed  ice  is • needed  around  the
impingers  to  maintain <20°C (68°F) at  the impinger  silica  gel
outlet in order to avoid excessive moisture loss.
1.5.4  Stopcock Grease -  Acetone  insoluble,  heat stable silicone
grease  is  required  unless  screw-on connectors  with Teflon  or
similar sleeves are used.
1.6  Reagents and Supplies (Sample Recovery and Analysis)
     Unless  otherwise indicated,  all  reagents  should  meet  the
specifications  of  the Committee  on Analytical  Reagents  of  the
American Chemical  Society (ACS);  otherwise, use  the best avail-
able grade.
1.6.1  Calcium  Oxide  (CaO)  - A reagent grade  or  a certified ACS
grade of CaO should contain £0.005% F.
l-6'2  Filters  - Whatman No. 541  (or equivalent) filters are re-
quired for filtration of the impinger contents and preparation of
the sample for analysis.
1.6.3  Phenolphthalein Indicator - A reagent grade or a certified
ACS  0.1%  phenolphthalein should be  a  1:1 ethanol-water mixture.
1.6.4  Sodium Hydroxide  - An ACS  reagent grade  (or the equiva-
lent) NaOH pellets  and  5M  NaOH reagent  grade or ACS is needed.
1.6.5  Sulfuric Acid  - An ACS  reagent grade  (or the equivalent)
concentrated H,SOA and 25%  (v/v)  reagent grade- or ACS is needed.  ,-
              ™  •*                                               j   *~~v *""}
                                                                O/7
o

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                                             Section No. 3.9.1
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 13 of 20

1.6.6   Total Ionic Strength Adjustment Buffer (TISAB)  - To  ap-
proximately  500  ml  of distilled water in a l-£ beaker, add 57 ml
of  glacial  acetic  acid,  58  g of  sodium chloride,  and 4  g of
cyclohexylene  dinitrilotetra acetic  acid (CDTA).  Stir  to dis-
solve.   Place  the beaker in a water  bath until  it cools.  Then,
slowly  add 5 M NaOH, while  measuring the pH  continuously with a
calibrated  pH-reference  electrode  pair,  until   the  pH  is 5.3.
Cool  to room temperature.  Pour into  a  l-£  flask,  and dilute to
volume  with  distilled water.  Commercially prepared TISAB buffer
may be  substituted for the above.
1.6.7   Fluoride Standard Solution - To  prepare  a  0.1M fluoride
reference  solution,  add 4.20 grams of reagent grade sodium fluo-
ride  (NaF)  to a  1-2  volumetric flask,  and  add  enough distilled
water  to dissolve  it.   Dilute  to volume with  distilled water.
The NaF must be  oven dried at  110°C for at  least 2  h prior to
weighing.
1.7  Analytical Equipment
1.7.1   Bunsen Burner  - A  Bunsen  burner capable of distilling 200
ml in <15 min is required for the boiling flasks.
1.7.2   Crucible - A  nickel  crucible  with a  capacity of  75 to
100 ml  is  needed to evaporate the water from the sample on a hot
plate.
     Upon  receipt,  check  for cracks  or manufacturing  flaws as
well as for  capacity.  If it does not meet specifications replace
or return it to the manufacturer.
1.7.3   Hot Plate - A  hot plate  capable  of 500°C  (932°F)  is re-
quired  for heating the sample in a nickel crucible.
     Check upon  receipt and before each use  for  damage.   Check
the heating  capacity  against a mercury-in-glass  thermometer.  If
inadequate,  repair or return the hot plate to the supplier.
1.7.4    Electric Muffle Furnace  -  An  electric   muffle   furnace
         — " -• -" --    -""                             t
capable  of heating  to 600°C (1112°F)  is  needed  to fuse the sam-
ple.
     Check the heating  capacity  against a mercury-in-glass ther-
mometer.   Replace  or return to  the manufacturer  any  unit which
does not meet specifications.                          ('

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                                             Section No.  3.9.1
                                             Revision No.  0
                                             Date January 4,  1982
                                             Page 14 of 20

1.7.5   Balance  - A  balance with  a  capacity of  300  g ±0.5  g  is
needed to determine moisture.
     Check for  damage against a  series  of  standard weights  upon
receipt and  before  each use.   Replace or return to the manufac-
turer if damaged or if it does not meet specifications.
1.7.6   Analytical Balance - An  analytical  balance  capable  of
weighing to  within  0.1  mg is  needed for preparation of the stan-
dard  fluoride  solution and the  analytical reagents.   Check the
balance frequently with Class  S weights.
1.7.7   Constant Temperature Bath  -  A water bath  is needed  to
maintain a constant room temperature  for  optimum measurement *of
the sample concentration.
i.7.8   Fluoride Ion Activity-Sensing Electrodes  - A  fluoride ion
(F~)  activity-sensing electrode  is  required in Method  13B for
determining  of  F*~  ion  activity  in  concentrations  of from  1  to
10~  mol/Ji (19,000  to 0.02  ppm).   The electrode should be usable'
from  a  pH  of 1 to  8.5 at 10~6 mol/£,  up to a  pH  of 11 at 10"2
mol/£ F~ concentration.   Due  to  the complexing of F~ below pH of
4 and to the limited  resistance of the electrode body to certain
concentrated acids, it is usually advisable to  adjust the pH of
strongly acidic samples.
     Check for  damage and F~ sensing  accuracy with a known con-
centration upon receipt and  before  each use.    If  not suitable,
replace or  return  to manufacturer.   Either a  single junction,
sleeve  type  reference  electrode  or a combination  type fluoride
ion-sensing electrode built into one unit may be used.
1.7.10  Electrometer  -  Either a  pH meter with  a millivolt  scale
capable of ±0.1-mV  resolution or  a ion meter made especially for
specific-ion use  is  needed to read the ion activity or  the F~
concentration.
1.7.11  Magnetic Stirrer - A magnetic stirrer and TFE* fluorocar-
bon-coated stirring bars  are needed  for  uniform  mixing  of the
sample solution.                                                      /""*\
1.7'. 12  Stopwatch or  Clock -  A stopwatch or a  clock is. needed to      V_y
check"minimum immersion time  of electrode in sample.
o
*Mention of  any trade name or  specific  product does not consti-
 tute endorcement by the Environmental Protection Agency.

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                                                      Section  No. 3.9.1
                                                      Revision No.  0
                                                      Date January  4,  1982
                                                      Page 15  'of 20
            TABLE 1.1  ACTIVITY MATRIX FOR PROCUREMENT OF APPARATUS
                                 AND SUPPLIES
Apparatus
Sampling

Probe liner
Probe nozzle
Pitot tube
'Differential
  pressure
  gauge (in-
  clined ma-
  nometer)
Filters
Acceptance limits
Specified material of
construction; equipped
with heating system
capable of maintaining
120°±14°C (248° ±25°F)
at the exit
Stainless steel (316)
with sharp, tapered
angle <30°; differ-
ence in measured diam-
eters £0.1 mm (0.004
in.); no nicks, dents,
or corrosion
Type S (Meth 2, Sec
3.1.2); attached to
probe with impact
(high pressure) opening
plane even with or
above nozzle entry
plane
Meets- criteria (Sec
3.1.2); agrees within
5% of gauge-oil
manometer
Capable of withstand-
ing temperatures to
135°C (275°F), 95%
collection efficiency
for 0.3 urn particles,
low F blank (<0.015
mg F/cm2)    ~~
Frequency and method
   of measurements
Visually check the
probe and run the
heating system
Visually check upon
receipt and before
each test; use a mi-
crometer to measure
ID before field use
after each repair
Visually check for
vertical and hori-
zontal tip alignments;
check the configura-
tion and the clear-
ances; calibrate
(Sec 3.1.2, Meth 2)
Check against a gauge-
oil manometer at a
minimum of three
points:   0.64(0.025);
12.7 (0.5); 25.4(1.0)
mm (in.) H20
Check each batch for
F blank values,
visibly inspect for
pin holes or flaws
Action if
requirements
are not met
Repair, return
to supplier,
or reject
Reshape and
sharpen, re-
turn to the
supplier, or
reject
Repair or re-
turn to sup-
plier
As above
Reject batch
(continued)

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                                                      Section No.  3.9.1
                                                      Revision No.  0
                                                      Date January 4, 1982
                                                      Page 16 of  20
                                                                  o
TABLE 1.1 (continued)
Apparatus
Filter holder
Condenser
Vacuum gauge
Vacuum pump
Barometer
Orifice meter
Dry gas meter
(continued)
Acceptance limits
Leak free; borosilicate
glass
Four impingers,  standard
stock glass;  pressure
drop not excessive
0-760 mm (0-30 in.) Hg,
±25 mm (1 in.) at
380 mm (15 in.) Hg
Leak free; capable of
maintaining flow rate
of 0.02-0.03 mVmin
(0.7 to 1.1 ftVmin)
for pump inlet vacuum
of 380 mm (15 in.) Hg
Capable of measuring
atmospheric pressure
±2.5 mm (0.1 in.) Hg
AH@ of 46.74± 6.35 mm
(1.84 ± 0.25 in.) H20
at 20°C (68°F);
optional
Capable of measuring
volume within ±2% at a
flow rate of 0.02
tnVmin (0.7 ftVmin)
Frequency and method
   of measurements
Visually check before
use
Visually check upon
receipt; check pres-
sure drop
Check against mer-
cury U-tube manometer
upon receipt
Check upon receipt
for leaks and capaci-
ty
Check against a mer-
cury-in-glass barom-
eter or equivalent;
calibrate (Sec 3.1.2)
Upon receipt, visual-
ly check for damage;
calibrate against wet
test meter
Check for damage upon
receipt and calibrate
(Sec 3.9.2) against
wet test meter
Action if
requirements
are not met
Return to
supplier
As above
Adjust or re-
turn to sup-
plier
Repair or re-
turn to sup-
plier
Determine cor-
rection fac-
tor, or reject
Repair or re-
turn to sup-
plier
Reject if dam-
aged, behaves
erratically,
or cannot be
properly ad-
justed
                                                                                  O
                                                                 o

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                                                      Section No.  3.9.1
                                                      Revision No. 0
                                                      Date  January 4,  1982
                                                      Page  17 of 20-
Table 1.1 (continued)
Apparatus
Thermometers
Sample Recovery

Probe liner and
  probe nozzle
  brushes
Wash bottles
Storage con-
  tainer
Graduated
  cylinder
Funnel
Rubber police-
  man
Acceptance limits
±1°C  (2°F) of true
value  in the range of
0° to  25°C (32° to 77°F)
for impinger thermometer
and ±3°C (S.A'F) of true
value  in the range of
0°C to 90°C (32° to
194°F) for dry gas
meter  thermometers
Nylon bristles with
stainless steel han-
dles; properly sized
and shaped
Polyethylene or glass,
500 ml
.High-density polyeth-
ylene, 1000 ml
Glass, Class A, 250 ml
Glass, Class A, diameter
100 mm; stem length
100 mm
Properly sized
Frequency and method
   of measurements
Check upon receipt
for dents or bent
stem, and calibrate
(Sec 3.9.2) against
mercury-in-glass
thermometer
Visually check for
damage upon receipt
Visually check for
damage upon receipt
Visually check for
damage upon receipt;
be sure caps make
proper seals
Upon receipt, check
for stock number,
cracks, breaks, and
manufacturer flaws
Visually check for
damage upon receipt
Visually check for
damage upon receipt
Action if
requirements
are not met
Reject if un-
able to cali-
brate
Replace or re-
turn to sup-
plier
As above
As above
As above
As above
As above
(continued)

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                                                      Section No.  3.9.1
                                                      Revision No.  0
                                                      Date January 4, 1982
                                                      Page 18 of  20
                                                                    o
TABLE 1.1 (continued)
Apparatus
Pipettes, volu-
  metric flask
  beaker, flask
  adapter, con-
  denser, con-
  nection tube,
  Erlenmeyer
  flask
Distallation
Apparatus

Bunsen burner
Crucible
Analytical
Equipment

Hot plate
Electric muffle
  furnace
Acceptance 1imits
Glass, Class A
Capable of distilling
220 ml in <15 min
Nickel material;  75-
100 ml
Heating capacity of
500°C (932°F)
Heating capacity of
600°C
Frequency and method
   of measurements
Upon receipt,  check
for stock number,
cracks, breaks and
manufacturer flaws
Visually check upon
receipt; check heat-
ing capacity, check
for damage
Check upon receipt
for cracks or flaws
Check upon receipt
and before each use
for damage; check
heating capacity
against mercury-in-
glass thermometer
Check upon receipt
and before each use
for damage; check
heating capacity
upon receipt against
mercury-in-glass
thermometer
Action if
requirements
are not met
Replace or re-
turn to sup-
plier
Replace
                                                                                   O
Replace or re-
turn to manu-
facturer
Replace or re-
turn to manu-
facturer
Replace or re-
turn to manu-
facturer
                                                                                  O
(continued)

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                                                      Section No.  3.9.1
                                                      Revision No. 0
                                                      Date  January 4,  1982
                                                      Page  19 of 20
Table 1.1 (continued)
Apparatus
Balance
Water bath
Fluoride ion
  activity-sen-
  sing electrode
Reference
  electrode
Electrometer
Reagents

Filters
Silica gel
Acceptance limits
Capacity of 300 g ±0.5g
Capable of maintaining
constant room tempera-
ture
Capable of measuring
F  concentration from
1 to 10-6 mol/£
(19,000 to 0.02 ppm)
Should provide stable
output
Capable of reading to
±0.1 mV resolution with
temperature compensa-
tion
Whatman No.
equivalent
541 or
Indicating Type 6-16
mesh
             Frequency  and  method
                of measurements
             Check for damage  and
             against series  of
             standard weights  upon
             receipt and before
             each use
             Check with  mercury-
             in-glass  thermometer
             Check for damage  and
             F  sensing accuracy
             with a known  con-
             centration upon re-
             ceipt and before
             each use
             Check visually for
             cracks or breaks
             Upon receipt and
             before each use,
             check for per-
             formance accuracy
             with a_known stan-
             dard F  solution
Visually check for
damage upon receipt'
             Upon receipt check
             label  for grade  or
             certification
                       Action  if
                       requirements
                       are  not met
                       Replace  or  re-
                       turn  to  manu-
                       facturer
                       Repair
                       Replace  or  re-
                       turn to  manu-
                       facturer
                       Replace or re-
                       turn to manu-
                       facturer
                       Replace or re-
                       turn to manu-
                       facturer
Replace or re-
turn to sup-
plier
                       Replace or re-
                       turn to manu-
                       facturer
(continued)

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                                               Section No.  3.9.1
                                               Revision  No.  0
                                               Date January 4,  1982
                                               Page 20 of 20
o
TABLE 1.1 (continued)
Apparatus
Reagents
Di stilled water
Crushed ice
Stopcock grease
Calcium oxide
powder
Phenolphthalein
Sodium hy-
droxide
Sulfuric acid
Fluoride stan-
dard solution
Acceptance limits
Must conform to ASTM-
01193-74, Type 3

Acetone insoluble, and
heat stable silicon
grease
Reagent grade or cer^
tified ACS
0.1% in 1:1 ethanol-
water mixture; reagent
grade or certified ACS
NaOH pellet 5M NaOH
reagent grade or cer-
tified ACS
Concentrated, reagent
grade or certified ACS;
25% (v/v) reagent grade
or ACS
Reagent grade or ACS;
1 M concentration
Frequency and method
of measurements
Check each lot
Check frozen condition
Upon receipt, check
label for grade or
certification
As above
As above
As above
As above
As above
Action if
requirements
are not met
Replace or re-
turn to manu-
facturer

As above
As above
As above
As above
As above
As above
                                                                        O
                                                                        o
                                                            (  F

-------
                                             Section No. 3.9.2
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 1 of 25
2.0  CALIBRATION OF APPARATUS
     Calibration of  apparatus  is  one of the most important func-
tions  in  maintaining  data  quality.   The  detailed  calibration
procedures in  this  section are designed for the equipment speci-
fied  in Method  13B and  described in  the previous  section.   A
laboratory  log  book  of  all  calibrations  must be  maintained.
Table  2.1 at  the  end  of this  section  summarizes  the  quality
assurance activities for calibration.
2.1  Metering System
2.1.1   Wet Test  Meter  - A wet test meter  with  a capacity of 3.4
m /h  (120  ft /h) will be needed to  calibrate the  dry gas me,ter.
Wet test meters are calibrated by the manufacturer to an accuracy
of +0.5%; the  calibration must be checked initially upon receipt
and  yearly  thereafter.   For  large wet test  meters (>3£/rev),
there  is  no convenient procedure for  checking the calibration;
for this reason, several methods are suggested,  and others may be
approved by the administrator.
     The initial  calibration • may be  checked by any  of the fol-
lowing methods:
     1.   Certification  from  the  manufacturer  that  the wet test
meter  is  within  +1% of  true  value at the wet test meter dis-
charge, so that only a leak check is needed.
     2.  'Calibration by  any primary air  or liquid displacement
method  that  displaces  at least  one  complete  revolution  of the
wet test meter.
     3.   Comparison  against a smaller wet test meter  that has
previously been  calibrated by a primary air or liquid displace-
ment method (Section 3.5.2).
     4.   Comparison against a dry  gas  meter that has previously
been calibrated  by  a primary air or  liquid displacement method.
     The calibration of the  test  meter should be checked annual-
ly.  This yearly calibration check can be made by the same method

-------
                                             Section -No.  3.9.2
                                             Revision No.  0
                                             Date January 4,  1982      f\
                                             Page 2 of 25             V_y

as that of the original calibration; however, the comparison pro-
cedure need not be recalibrated if the check is within +1% of the
true value; if not within ±1%, either the comparison procedure or
the wet test  meter  must be recalibrated against a primary air or
liquid displacement method.
2.1.2  Sample Meter System - The sample meter system—consisting
of  the  pump,   vacuum  gauge, valves,  orifice meter, and  dry gas
meter—should  be initially  calibrated  by  stringent  laboratory
procedures before it is used in the field.  After initial accept-
ance, the  calibration should be rechecked  after each field test
series.  The  recheck  procedure can be used by  the tester often
and with  little time  and  effort  to  ensure  that calibration has
not changed.  When the quick check indicates that the calibration
factor has  changed, the tester must again use the complete labo-
ratory  procedure  to   obtain  a  new  calibration  factor.  ' After      (j
recalibration,  the  metered  sample  volume must  be  multiplied by      ^-^
either the  initial  or  the  recalibrated calibration factor—that
is, the one that yields the lower  gas volume  for each test run.
     Before initial calibration, a leak check is recommended, but
it  is  not mandatory.   Both  positive  (pressure)  and  negative
(vacuum) leak checks  should be performed.   Following is a pres-
sure  leak-check  procedure  for  checking  the metering system from
the quick disconnect inlet to the orifice outlet and for checking
the orifice-inclined manometer:
     1.   Disconnect  the orifice  meter  line from the downstream
orifice pressure tap   (the  one closest to  the exhaust  of the
orifice),  and plug this tap  (Figure 2.1).
     2.   Vent the negative side of the inclined manometer to the
atmosphere.   If the manometer is equipped with a three-way valve,
merely  turn  the valve that  is  on  the  negative  side  of the
orifice-inclined manometer to the vent position.                       -^
     3.   Place  a one-hole  rubber  stopper  with a  tube  through     (  j
its hole  into the  exit of the orifice,  and connect  a  piece of
rubber  or  plastic  tubing  to the tube,  as  shown  in Figure 2.1.

-------
                 RUBBER
                 TUBING
RUBBER   ORIFICE
STOPPER
BLOW INTO TUBING UNTIL
MANOMETER READS 127  to
178 mm ( 5 TO  7 in.)
                                                                                                  MAIN VALVE
                                                                                                   CLOSED
                          ORIFICE/
                         MANOMETER
                          Figure 2.1.  Positive leak check  of metering system.
                                                                                                                    B> P> (T> fl>
                                                                                                                    iQ rt < O
                                                                                                                    fl> fO H-rt
                                                                                                                        w H-
                                                                                                                        H-O

                                                                                                                    os P3
                                                                                                                        O •
                                                                                                                          vo
                                                                                                                      CO
                                                                                                                      ro

-------
                                             Section No.  3.9.2
                                             Revision No.  0
                                             Date January 4,  1982
                                             Page 4 of 25

     4.   Open the  positive side of the manometer  to the "read-
ing"  position;  if  the  manometer  is  equipped  with  a  three-way
valve, this will be the line position.
     5.   Plug the  inlet  to the vacuum pump.  If a quick discon-
nect with  a  leak-free  check valve is used on the control module,
the inlet will not have to be plugged.
     6.   Open the main valve and the bypass valve.
     7.   Blow into  the tubing connected to the  end of  the ori-
fice until a pressure of 127 to 178 mm (5 to 7 in.) H20 has built
up in the system.
     8.   Plug or  crimp  the tubing to  maintain  this  pressure.
     9.   Observe the pressure  reading for 1 min.  No noticeable
movement in  the manometer fluid level  should occur.  A bubbling-
type  leak-check  solution  may  aid  in  locating  any leak  in the
meter box.                                                           C)
     After the metering system is determined to  be leak free by
the positive leak-check procedure, check the vacuum system to and
including the pump.
     1.   Plug the  air  inlet to the meter box.   If a quick dis-
connect with a leak-free stopper system is on the meter box, the
inlet will not have to be plugged.
     2.   Turn the  pump  on and pull  a  vacuum  within 7.5  cm (3
in.) Hg of absolute zero.
     3.   Observe the   dry gas  meter.  If  leakage  is  > 0.00015
m3/min  (0.005  fts/min), find and minimize  the  leak(s)  until the
above specifications are satisfied.
     For  metering  systems  with diaphragm pumps,  the leak-check
procedures above  will  not  detect  leakages within  the pump; the
following procedure is suggested:
     1.  Make  a  10-min  calibration  run at  0.00057 ms/min  (0.02
ft3/min).                                                            ^^^
      2.  At the  end  of the run, find the difference between the    (  J
measured wet test meter and the dry gas meter volumes, and divide
the difference by 10  to get the leak rate.  The leak rate should
not exceed 0.00057 ms/min  (0.02 ft3/min).                   •

-------
                                             Section No. 3.9.2
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 5 of 25

2.1.2.1  Initial calibration  -  The  dry gas meter and the orifice
meter can be  calibrated simultaneously,  and both should be cali-
brated  when  first  purchased  and  any time  the posttest  check
yields  a Y  outside  the range of the calibration factor Y +0.05Y.
     Use a  calibrated wet  test meter (properly sized,  with +1%
accuracy) to  calibrate  both the dry  gas meter and  the orifice
meter (Figure 2.2) in the following manner:
     1.   Leak check  the metering system (Subsection 2.1.2), and
eliminate any leaks before proceeding.
     2 .   Connect the air  outlet of  the wet test meter  to the
needle  valve  at the  inlet side  of the  meter box  (Figure 2.2).
     3.   Run the pump  for 15 min with the orifice meter differ-
ential  (AH)  set at 12.7 mm  (0.5 in.) H2O to allow  the pump to
warm up and to  permit the interior surface of the wet test meter
to be wetted.
     4.   Adjust the needle valve so that the vacuum gauge on the
meter box is  between  50 and 100 mm  (2 to 4 in. ) Hg during cali-
bration.
     5.   Record the  required data  on Figure 2.3A or 2.3B, using
sample volumes as shown.
     6.   Calculate Y.  for  each of  the six runs, using the equa-
tion in Figure  2.3A  or 2.3B, and 'record  the  results  on the  form
in the space provided.
     7.   Calculate the average  Y  (calibration factor)  for the
six runs,  using the following equation:
                  v
                  * ~
Record  the  average in  the  space provided  on  Figure 2.3A  or
2.3B.
     8.   Clean,  adjust,  and  recalibrate,   or   reject  the  dry
gas  meter if  one  or  more  values  are outside  the  interval  Y
10.02Y;  otherwise,  the  average  Y is  acceptable and  should  be
used for future checks and test runs .

-------
   ORIFICE
X__XVCTT
IW
   ORIFICE
                                                                                             AIR IKLET
                                                                             LEVEL ADJUST
                Figure 2.2.   Sample  meter system calibration setup,
                                                                                                 HATER
                                                                                                 LEVEL
                                                                                                 GAUGE
                                                                                            HATER OUT
                                                                                                              hJ t> Jd W
                                                                                                              Q) P) 0 Q
                                                                                                             iQ rf < O
                                                                                                              0) a t->- rt
                                                                                                                r. W H-
                                                                                                              <*£H-O
                                                                                                                r; o P
                                                                                                              i^ *-* ^
                                                                                                                (a
                                                                                                                  o
                                                                                                                    10
                                                                                                                    vo
                                                                                                                oo
                                                                                                                to
        O
                                                           o
o

-------
                                             Section No. 3.9.2
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 7 of 25
Date
             S&
             -
Barometric pressure, P, = c>?9,
                                     Meter box number   f=-H-


                             in.  Hg   Calibrated by
Orifice
manometer
setting
(AH),
in. H20
0.5
1.0
1:5
2.0
- 3.0
4.0
Gas volume
Wet test
meter
 <'. + 46«
^ f£9, U V-") (S'<4 9^>
•T. / »)- W9 x 67^ /6"5A S")





.... 0.0317 AH (^w + 46°') 6
^i - Pb (t, + 460) [ Vw J
($>o3n)C<3~S^r?fr3j. S")^/p 75- ¥
4?3. (a*^)C .^^^ 1 5 -J





alf there is only one thermometer on the dry gas meter, record the temperature
under t,.
d
Figure 2.3A.   Dry gas meter  calibration data  (English units).
               (front side)

-------
Nomenclature :

  V  = Gas volume passing through the wet test meter, ft3.
   w

  V, = Gas volume passing through the dry gas meter, ft3.

  t  "= Temperature of the gas in the wet test meter, °F.
   W

 t,  = Temperature of the inlet gas of the dry gas meter, °F.


 t,  = Temperature of the outlet gas of the dry gas meter, °F.
   o

  t, = Average temperature of gas in dry gas meter, obtained by average t,  and
       t    °F                                                            i
         CD n-rt
                                                                                             CD Q H- O
   6 = Time for each calibration run, min.                                                   o S § 3
                                                                                             Hi C   25
  P, = Barometric pressure, in. Hg.
         Figure 2.3A.  Dry gas meter calibration data  (English units).   (backside)
                                                                                                  u>
                                                                                                o •
                                                                                              00
                                                                                              Jvj
        ooo

-------
                                                Section No. 3.9.2
                                                Revision No. 0
                                                Date January 4, 1982
                                                Page 9 of 25
Barometric pressure, P, =
        Meter box number   "p-hi -

mm Hg    Calibrated by 	
Orifice
manometer
setting
(AH),
mm HgO
10
25
40
50
75
100
Gas volume
Wet test
meter
'/ C«29/ y





s only one thermometer on the d
,, 0.00117 AH ^w + 273^ 6
•** - Pb (td + 273) [ Vw J
(&.OO/1'7) (/(-^i f~C.? £ /O'£>«a}~
C73(i)C2lT) 1 OtJS'Z _J





ry gas meter, record the temperature
    Figure 2.3B.  Dry gas meter calibration data (metric units).
                   (front side)

-------
                                                                         and
Nomenclature:

  V  = Gas volume passing through the wet test meter, m3.
   w

  V, = Gas volume passing through the dry gas meter, m3.

  t  = Temperature of the gas in the wet test meter, °C.
   Vr

 t,  = Temperature of the inlet gas of the dry gas meter, °C.


 t,  = Temperature of the outlet gas of the dry gas meter, °C.
   o

  t, = Average temperature of gas in dry gas meter, obtained by average of t,



  AH = Pressure differential across orifice, mm H2O.

  Y. = Ratio of accuracy of wet test meter to dry gas meter for each run; tolerance Y.  =
       Y+0.02 Y.

   Y = Average ratio of accuracy of wet test meter to dry gas meter for all six runs.

AH@. = Orifice pressure differential at each flow rate that gives 0.021 m3 of air  at standard
       conditions for each calibration run, mm H2O; tolerance AH@- = AH@±3.8 mm H2O
       (recommended).
                                                                                            hj o to cr.
 AH@ = Average orifice pressure differential that gives 0.021 m3 of air at standard con-    ^ j»«| flj
       ditions for all six runs, mm H2O; tolerance AH@ = 46.74 +6.3 mm H2O (recommended)    CD ro n-rt
                                                               —                               W H
                                                                                            M C_| H- O
   6 = Time of each calibration run, min.                                                   ° Ej g 3
                                                                                            o a  a
  P. = Barometric pressure, mm Hg.                                                          H, PJ z p
                                                                                          OJ
                                                                                         o •
                                                                                          vo
  Figure 2.3B  Dry gas meter calibration data  (metric units).   (backside)              £
                                                                                       00 '
                                                                                       M

ooo

-------
                                             Section No. 3.9.2
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 11 of 25

     9.   Calculate  AH@^  for  each  of the  six  runs,  using  the
equation  in  Figure 2.3A  or  2.3B,  and record  the  results on the
form in the space provided.
    10.   Calculate  the  average AH@ for the six runs,  using the
following equation:

                    AH@- + AH@  + AH@, + AH@A + 'AH@C + AH®.
              AH@ = 	±	2	3^	4	5	6 .
                                      D
Record the average  in the space provided on Figure 2.3A or 2.3B.
    11.   Adjust the orifice meter or reject it if AH@. varies by
more than ±3.8  mm (0.15 in.) H20 over the  range of 10 to 100 mm
(0.4 to  4.0  in.) H2O;  otherwise,  the average  AH@ is acceptable
and should be used for subsequent test runs.
2.1.2.2   Posttest .calibration check  -  After  each  field  test
series, conduct  a  calibration  check of the metering system (Sub-
section 2.1.2) except for the following variations:
     1.   Three calibration runs at a single intermediate orifice
meter  setting  may be  used  with  the  vacuum set  at  the maximum
value  reached  during the  test series.  The  single intermediate
orifice meter setting should be based on the previous field test.
To adjust the  vacuum,  insert a valve  between  the  wet test meter
and the inlet of the metering system.
     2.   If a  temperature-compensating  dry gas  meter was used,
the calibration  temperature  for the dry gas meter must be within
+6°C (10.8°F)  of the average  meter temperature during the test
series.
     3.   Use Figure  2.4A or 2.4B  to  record  the  required data.
     If  the  recalibration  factor  Y  deviates  by  <5%  from  the
initial Y  (determined  in Subsection  2.1.2),  the  dry  gas meter
volumes  recorded during  the  test  series  are acceptable;  if  Y
deviates  by   >5%,  recalibrate  the  metering  system  (Subsection
2.1.2),  and  use the  coefficient  (initial  or  recalibrated) that
yields the lower gas volume for each test run.
     Alternate procedures—for  example,  using the  orifice meter
coefficients—may be used, subject to the approval of the admini-
strator.

-------
Test numbers /)<6  /~3
Barometric pressure, P
Date 5~/3-$O    Meter box number
                                                                   ~ 7
                                                                                  Plant  flcme.
          in. Hg   Dry gas meter number
                                                                            Pretest Y
                                                                                                 p.
Orifice
manometer
setting,
(AH),
in. H20
"AW


Gas volume
Wet test
meter
(vw),
ft3
10
10
10
Dry gas
meter
,
°F
7«


Dry gas meter
Inlet
°F
^3


Outlet
(td),
o
°F
75"


Average
°F
79


Time
(9),
nin
7*35-


Vacuum
setting,
in. Hg
3-o



Yi
0-95-7


Y.
V P. (t. + 460)
w b x d '
VIP + ... ._ iff i /inni

/o (*l& • 7»OC*'5~.3<50
/0.*A3(Z9.7*+-^)(S3*


Y =
V
If there is only one thermometer oh the dry gas meter, record the temperature under t..
 V  = Gas volume passing through the wet test meter, ft3.
  w
 V. = Gas volume passing through the dry gas tneter, ft3.
 t  = Temperature of the gas in the wet test meter, °F.
  W
t.  = Temperature of the inlet gas of the dry gas meter, °F.
t.  = Temperature of the outlet gas of the dry gas meter, °F.
  o
 t. = Average temperature of the gas in the dry gas meter, obtained by the average of
 AH = Pressure differential  across orifice, in. H20.
 Y. = Ratio of accuracy of wet test neter to dry gas meter for each run.
  Y = Average ratio of accuracy of wet test meter to dry gas meter for all three runs;
      tolerance = pretest Y +0.05Y
 P. = Barometric pressure, in. Hg.
  8 = Time of calibration run, nin.
          Figure 2.4A.  Posttest dry gas meter calibration data form (English units).
                                                                                                              D» a-
                                                                                                 and  t.  ,  °F.  ° " K"
                                                                                                      QO      M Ci H-
                                                                                                      u      ro p o
                                                                                                                    n>
                                                                                                              H|P»
                                                                                in
                                                                                                                    U>
                                                                                                                    •
                                                                                                                    vo
                                                                                  vO
                                                                                  OJ
       O
                                                    o
                                                                               o

-------
lest numbers
1-3     Date  S-/3-SO     Meter  box number
Barometric pressure, P.  =
                mm  Hg    Dry  gas  meter number   /r/y?- 7
 Plant Acme, fkcoer
Pretest Y
Orifice
manometer
setting,
(AH),
mm H20
3&>


r Gas volume
Wet test
meter
(Vw>,
m3
0.30
0.30
0.30
Dry gas
meter
(vd),
m3
24. / 744
l
°C
33.5"


Outlet
(td),
o
°C
AL5"


Average
(td),*
°C
£3.5"


Time
(e),
min
I3.S-0


Vacuum
setting,
mm Hg
75"



Y.
o. <&&>


Yi
Vw Pb (td * 273)
V /P. + AH Vt + 273\
dlb Ti^Aw )
0.30 C73o)Ca H-rt
                                                                                           en H-
                                                                                       H ^4 H- O
                                                                                       O C   2
                                                                                       HI P a o
                                                                                           O •
                                                                                       Ul
                                                                                             (A)
                                                                                             to
                                                                                         CO
                                                                                         ro

-------
Section No. 3.9.2
Revision No. 0
Date January 4,  1982
Page 14 of 25
                                                                       o
                           o
2.2  Temperature Gauges
2.2.1   Impinger Thermometer - The  thermometer  used to  measure
temperature of the gas leaving the impinger train should initial-
ly be  compared with  a  mercury-in-glass  thermometer which meets
ASTM  E-l  No.   3C  or  3F specifications.   The  procedure is  as
follows:
     1.   Place  both  the  reference  thermometer  and  the  test
thermometer  in  an  ice  bath,  and  compare  readings after  they
stabilize.
     2.   Remove the  thermometers from the  bath,  and allow both
to come  to room temperature,  compare  readings  after they stabi-
lize.
     3.   Accept the  test  thermometer if both of  its  readings
agree within 1°C  (2°F)  of the reference thermometer reading.  If
the  difference  is  greater  than ±1°C  (2°F),  either adjust and
recalibrate it until agreement is obtained, or reject it.
2.2.2  Dry Gas Thermometers - The  thermometers used to measure
the  metered gas sample  temperature  should initially be compared
with  a mercury-in-glass  thermometer,  using  a similar procedure.
     1.   Place  a  dial type or  an  equivalent  thermometer  and a
mercury-in-glass thermometer in  a  hot water bath,  40°  to 50°C
(105° to  122°F); compare the readings after the bath stabilizes.
     2.   Allow both thermometers to come to room temperature and
compare readings after they stabilize.
     3.   Accept the  dial type  or  equivalent thermometer if the
values agree  within 3°C(5.4°F) at both points  or  if the temper-
ature  differentials  at both points  are within ±3°C(5.4°F); tape
the  temperature  differential  to  the thermometer/ and record them
on the pretest sampling check form (Figure 3.1 of Section 3.9.3).
     4.   Before  each  field trip,   compare   the reading  of the
mercury-in-glass thermometer at room temperature with that of the
meter  system  thermometer;  the  values or the  corrected values       [)
should agree  within ±6°C  (10.8°F)  of one another,  or  the meter       \*-S
thermometer  should  be  replaced or  recalibrated.   Record  any
correction/factors on Figure 3.1 or on^a similar form.          /  Ac/
                   M'1

-------
                                             Section No. 3.9.2
                                             Revision No. 0
                                             Date January 4,  1982
                            i                 Page 15 of 25

2.2.3   Stack Temperature  Sensor -  The  stack  temperature  sensor
should  be  calibrated upon  receipt  or checked before  field  use.
Each  sensor should  be  uniquely marked for  identification.   The
calibration  should  be performed at three points  and then extra-
polated  over  the  temperature  range  anticipated during  actual
sampling.   For the  three-point  calibration,  a reference mercury-
in-glass thermometer  should be  used.   The following procedure is
recommended  for  calibrating  stack  temperature  sensors (thermo-
couples and thermometers) for field use,
     1.   For  the  ice  point  calibration,   form a  slush  from
crushed  ice  and  water  (preferably  deionized distilled) in an
insulated  vessel  such  as  a  Dewar  flask;   being sure  that the
sensor  does not  touch  the  sides of  the  flask,  insert the stack
temperature  sensor  into the  slush  to a depth of at least 2 in.
Wait 1 min to achieve thermal equilibrium, and record the readout
on  the  potentiometer.    Obtain three  readings  taken  in  1-min
intervals.  Note;   Longer times may be required to attain thermal
equilibrium with thick-sheathed thermocouples.
     2.   Fill a  large  Pyrex  beaker with water to a depth >4 in.
Place several boiling chips in  the water, and bring the water to
a full  boil using  a hot plate  as  the  heat  source.   Insert the
stack temperature sensor(s) in the boiling water to a depth of at
least 2  in.,  taking care not to touch the sides or bottom of the
beaker.
     Alongside  the  sensor(s),   an.  ASTM  reference  thermometer
should  be  placed.   After  3  min,   both instruments  will  attain
thermal equilibrium.  Simultaneously record temperatures from the
ASTM reference thermometer and the stack temperature sensor three
times at 1-min intervals.
     If  the entire  length of the mercury column  in  the thermom-
eter  cannot be immersed,  a  temperature  correction will  be re-
quired to give the correct reference temperature.
     3.   For a thermocouple, repeat  Step 2  with a liquid (e.g.,
cooking -oil)  that  has  a boiling  point  150°  to 250°C  (300° to

-------
                                             Section No. 3.9.2
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 16 of 25

500°F),  and  record  all  data on  Figure  2.5.   For thermometers
other than thermocouples, either repeat Step 2 with a liquid that
boils  at the maximum  temperature  that the thermometer  is to be
used or place the stack thermometer and the reference thermometer
in  a  furnace or other device  to  attain the desired temperature.
Note;   if  the thermometer  is  to be used  at temperatures higher
than the reference thermometer will record,  calibrate the stack
thermometer  with  a  thermocouple  previously  calibrated  by  the
above procedure.
     4.   If  the  absolute temperature  of  the reference thermom-
eter and the thermocouple(s)  agree  within ±1.5%  at  each of the
three  calibration  points, either  plot the data on' linear graph
paper  and draw  the best-fit line between the points or calculate
the linear  equation  using the method  of  least-squares.  For the
thermocouple, the  data may be  extrapolated above  and below the       C)
calibration points to  cover the manufacturer's suggested range,"       ^-""^
for the portion of  the  plot (or equation)  that  agrees within
1.5%  of the  absolute  reference  temperature,  no  correction is
needed,  but  for  all  other portions  that  do not  agree within
±1.5%,  use the plot (or equation) to correct the data.
     If  the  absolute  temperatures of  the  reference thermometer
and stack temperature  sensor  (other  than the thermocouple) agree
within ±1.5%  at each  of the three points, the thermometer may be
used for testing without applying any correction factor over the
range of calibration points,  but the data cannot be extrapolated
outside the calibration points.
2.3  Probe Heater
     The probe  heating system should  be  calibrated before field
use according to the procedure in APTD-0576.*1  Probes constructed
according to  APTD-05813  need not be calibrated  if the curves of
APTD-05764 are used.                                                     ^^^
2.4  Barometer                                                          f   j
     The field barometer  should  be adjusted initially and before
each test  series  to  agree within ±2.5 mm  (0.1 in-.)  Hg  of  the
mercury-in-glass barometer  reading or with the value reported by ,

-------
                                                    Section No. 3.9.2
                                                    Revision No.  0
                                                    Date January  4,  1982
                                                    Page 17 of 25
Date
Thermocouple  number
Ambient temperature

Calibrator
C  Barometric pressure
                        J. £ 7
in.  Hg
Reference:   mercury-in-glass

 other
Reference
point
number
0°
100'

Source3
(specify)
•/C£ «>*TtA,
Goi/i'**} Utfi'T£&
DOI/I'A/Q C It &->>/4
Oil
Reference
thermometer
temperature ,
°C
r -
/£>/. 5~'

Thermocouple
potentiometer
temperature,
°C
/'
/*''

Temperature.
difference,
• 	 	
OJ1-

 Type of calibration system used.
3f(ref temp.  °C + 273) - (test thermom temp, °C + 273)1
 L              ref temp, "C + 273                  \
         Figure  2.5  Stack temperature sensor calibration data form.

-------
o
                                             Section No.  3.9.2
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 18 of 25

a  nearby  National  Weather  Service  station  and corrected  for
elevation.  Correction  for the elevation  difference  between the
station  and  the sampling  point should be  applied at a  rate of
-2.5 mm Hg/30 m  (0.1  in.  Hg/100 ft).  Record  the results on the
pretest sampling check form (Figure 3.1).
2.5  Probe Nozzle
     Probe nozzles  should be calibrated initially before use in
the field.
     1.   Use a micrometer to measure the ID of the nozzle to the
nearest 0.025 mm (0.001 in.).
     2.   Make three measurements  using  different diameters  each
time.
     3.   Average the three measurements.   The difference between
the high  and  the  low  numbers should not be  <_0.1 mm (0.004 in.).
     4.   Label each nozzle  permanently  and uniquely for Identi-       x—x
fication.                                                               \^/
     5.   Record the  data on Figure 2.6,  the nozzle calibration
form.    If nozzles become  nicked,  dented,   or  corroded,  reshape,
sharpen, and recalibrate before use.
2.6  Pitot Tube
     The  Type  S  pitot  tube  assembly should be  calibrated using
the procedure in Section'3.1.2, Method 2.
2.7  Trip Balance
     The  trip balance  should  be  calibrated  initially  by using
Class-S  standard  weights,  and  it  should agree  within  ±0.5  g of
the standard  weight.   Adjust or return the balance to the manu-
facturer if limits are not met.
2.8  Fluoride Electrode
     The  fluoride  (F~)  electrode  should be calibrated daily, and
checked  hourly  against serial  dilutions   of  the  0.1M  fluoride
standard solution.  Use the following procedure  to prepare and to
measure the concentration  of the dilutions.                             f  j
     1.   Pipette  10 ml   of  0.1M NaF  into a 100-ml volumetric
flask,  and  dilute  to   the  mark  with  distilled  water  to get
0.01M  NaF;,'Cdilute 10 ml  of the  0.01M  solution to make  a 0.001M    ; :' '

-------
                                           Section No. 3.9.2
                                           Revision No. 0
                                           Date January 4,  1982
                                           Page 19 of 25
Date
                  1 tO
Calibrated by
Nozzle
identification
number
37
Nozzle Diameter3
jnar?ii.)
/< "^ *-T" /
U- ^° /
D2,
jffin (in. )

D3,
mm (in. )

AD,b
mm (in. )

D c
avg

where:

"D
  1,2,3,
      AD =
           three different nozzles diameters, mm (in.); each
           diameter must be within (0.025 mm) 0.001 in.

           maximum difference between any two diameters, mm (in.),
           AD £(0.10 mm) 0.004 in.
     avg
         = average of D,,  D2/ and
            Figure 2.6  Nozzle calibration data form.

-------
                                             Section No.  3.9.2
                                             Revision No.  -<
                                             Date January 4,  1982
                                             Page 20 of 25

solution; continue  in  the  same manner to get the  0.001M  and the
0.00001M dilutions.
     2.   Pipette  50  ml  of  each NaF  dilution  into  separate
beakers.
     3.   Add 50 ml of TISAB to each beaker.
     4.   Immerse  the  electrode  into the  most dilute  standard
solution, and measure  the  developed potential while stirring the
solution  with  a  magnetic  stirrer.   Note;   Avoid  stirring the
solution  before immersing  the electrode  because  entrapped air
around  the  crystal  can cause  erroneous  readings  or needle fluc-
tuations .
     5.   Keep  the  electrodes immersed  in  the  solution  3 min in
order  for  it to stabilize before  taking a  final positive milli-
volt reading.
     6.   Record the reading  on the laboratory form, Figure 2.7,
and remove the electrode from the sample.
     7.   Soak . the  electrode  for  30  s  in  distilled  water, and
then blot it dry.
     8.   Plot the millivolt  value on the  linear axis of semilog
graph  paper  and plot the known concentrations  of fluoride stan-
dards  on the log axis  as  shown in Figure  2.8.   Note ;   Plot the
nominal  value  for  concentrations  of the  standards on  the log
axis;  for  example,  when 50  ml of the 0.01M standard is diluted
with 50 ml TISAB, the concentration is plotted as 0.01M.  Measure
the most dilute standard first and the most concentrated standard
last,  as shown  on  Figure 2.8, to get a  straight-line calibration
curve  with  nominal concentrations  of  0.00001,   0.0001,  0.001,
0.01, and 0.1M NaF.   To obtain the required precision, use 4 or 5
cycle semilog paper similar to that in Figure 2.8.
     To  check the accuracy  of the calibration curve, prepare and
measure  a  control  sample  (Section 3.9.5).    Prepare fresh stan-
dardizing solutions  of  <_0.01M NaF daily, and store  the solutions
in polyethylene or polypropylene contains.
     The fluoride electrode  should be .checked periodically after
repeated  use for  responsiveness  and sensitivity.   Compare the
    o
    o
 (\j
\r

-------
                                                    section No.  3.9.2
                                                    Revision No.  0
                                                    Date January 4,  1982
                                                    Page 21 of 25
                            LABORATORY WORKSHEET
Date standards  prepared _

Temperature of  standards
                                , S* C.
                                                     Date   J- S~ SO
Electrode  number
Standard number
/
£
3
4
5"
£
Control Sample
Concentration (M)
0.000001
0.00001
0.0001
0.001
0.01
0.1
o.oor
Electrode potential (mV)
—
300
A<*7
£01
1*1
10
ItU
Note:   The  concentration of the control  sample determined from the calibration
curve  must  be  between 0.002M and 0.01M.
Signature  of  analyst

Signature  of  reviewer
          Figure 2.7.  Fluoride calibration data form.   (Method  13B)
                                                                  i  11

-------
                                                      Section No.  3.9.2
                                                      Revision No.  0
                                                      Date January 4,  1982
                                                      Page  22 of 25
                                                                      o
     50
    100
    150
I   200
    250
Date .
Sample temp
Analyst  T"  Loco n
             Reviewer k)  M/ t£f/u> / /
    300
       10
                                                       Results
                                     Mo1 a ri ty

                                     0.00001M
                                     0.0001M
                                     0.001M
                                     0.01M
                                     0.1M
                                     Control
                                       sample
                        -4
                            -3
         10                10

               FLUORIDE MOLARITY (M)
10
  -2
        nW

        3 o
10
  -1
                                                                                   O
               Figure 2.8.   Fluoride calibration curve,  Method 13B.
                                                                                  O
                                                                 < K

-------
                                             Section No. 3.9.2
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 23 of 25

electrode responses or millivolt readings of samples or standards
of the same  fluoride  concentration.   For equal concentrations of
fluoride, the  electrode response should  remain  stable with each
analysis, if not, repair or replace the electrode.
     Certain specific-ion meters designed specifically for fluoride
electrode use  give direct readouts  of F~ concentrations.  These
meters may  be  used over narrow concentration ranges.   Calibrate
the meter according to manufacturer's directions.

-------
                                                     Section No. 3.9.2
                                                     Revision  No. .0
                                                     Date January 4,  1982
                                                     Page 24 of 25
                                                                   o
         TABLE 2.1.   ACTIVITY MATRIX  FOR CALIBRATION OF EQUIPMENT
Apparatus
Wet test meter
Dry gas meter
Thermometers
Barometer
Probe nozzle
(continued)
Acceptance limits
Capacity of >3.4 m3/h
(120 fts/h)f accuracy
within ±1.0%
Y. = Y ± 0.02 Y at
flow rate of 0.02 -
0.03 mVmin (0.7 -
1.1 ftVmin)
Impinger thermometer
+1°C (2°F); dry gas
meter thermometer
+3°C (5.4°F) over
applicable range
+2.5 mm (0.1 in.) Hg of
mercury-in-glass barom-
eter
Average three ID mea-
surements of nozzle;
difference between high
and low <0.1 mm
(0.004 in.)
Frequency and method
    of measurement
Calibrate initially
and yearly by liquid
displacement
Calibrate with wet
test meter initially
to agree within Y ±
0.02 Y and when post-
test check is not
within Y ± 0.05 Y
Calibrate each ini-
tially against a
mercury-in-glass
thermometer; before
field trip compare
each with mercury-
in-glass thermometer
Calibrate initially
vs mercury-in-glass
barometer; check
before and after
each field test
Use a micrometer to
measure to near-
est 0.025 mm (0.001
in.)
Action if
requirements
are not met
Adjust to
meet specifi-
cations, or
return to
manufacturer
Repair or re-
place, and
then recali-
brate
Adjust, de-
termine a
constant cor-
rection fac-
tor, or re-
ject
Adjust to
agree with
certified
barometer
Recalibrate,
reshape, and
sharpen when
nozzle be-
comes nicked,
dented, or
corroded
O
                                                                   o
                                                                      ,J

-------
                                                     Section  No. 3.9.2
                                                     Revision No.  0
                                                     Date January  4,  1982
                                                     Page 25  of 25
Table 2.1 (continued)
Apparatus
Stack tempera-
  ture sensor
Trip balance
Pi tot tube
Fluoride
  electrode
Acceptance limits
±1.5% of average stack
temperature, °R
Standard Class-S
weights within ±0.5 g
of stated value
Type S; initially
calibrated according to
Section 3.1,  Meth 2;
tube tips undamaged
Calibration curve plot-
ted with F  standard
solutions of 0.1M,
0.01M, 0.001M,
0.0001M, and 0.00001M
and corresponding mV
reading on semi log
graph paper; stable
electrode response
Frequency and method
    of measurement
Calibrate initially;
check after each
field test
Verify calibration
when first purchased,
any time moved or
subject to .rough
handling, and during
routine operations
when not within
± 0.5 g
Visually check
before each field
test
Calibrate with each
use and every hour
of continuous use;
check response
stability of elec-
trode after re-
peated use
Action if
requirements
are not met
Adjust or
reject
Have the
manufacturer
recalibrate
or adjust
Repair or
replace
Repair or
replace

-------
o
o
o

-------
                                             Section No. 3.9.3
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 1 of 6
3.0  PRESAMPLING OPERATIONS
     The quality assurance  activities  for presampling operations
are  summarized  in  Table  3.1  at  the  end of this  section.   See
Sections 3.0.1  and 3.0.2, of  this Handbook  for general informa-
tion on  preliminary site visits.   See Section 3.4.3  (Method 5)
for more detailed  and  specific information of presampling opera-
tions for sampling  equipment similar to the Method 13 equipment.
3.1  Apparatus Check and Calibration
     Pretest checks must be made on most of the sampling apparat-
us.  Figure  3.1 should  be  used  to record  data on  the pretest
calibration checks.  Figure 3.2  in  Section  3.4 of  this Handbook
is recommended to aid the tester in preparing an equipment check-
list, status form,  and packing list.
3.1.1  Sampling Train - A schematic of the EPA Method 13 sampling
train (Figure  1.1)  should be  used  for assembling the components
and for  checking for compliance  (specifications in the Reference
Method,  Section 3.9.10).
3.1.2  Probe and Noz'zle - Clean the  probe and  the  nozzle inter-
nally by brushing  first with tap  water, then with deionized dis-
tilled water, and  finally with acetone; allow both to dry in the
air.  The probe  should be sealed  at .the  inlet  or tip;  should be
checked  for leaks  at a vacuum of 380  mm  (15 in.) Hg; and should
be leak free under these conditions.  The probe liner, in extreme
cases,  can be cleaned with stronger reagents; in either case, the
objective is  to leave the  liner  free  from  contaminants.   Check
the probe's  heating system to see that it is operating properly
and that it prevents moisture condensation.
3.1.3  Impingers, Filter Holders,  and Glass Connectors    -    All
glassware should be cleaned  first  with detergent  and  tap  water
and then with deionized distilled water.  All glassware should be
visually inspected  for cracks or  breakage and then  repaired or
discarded if  defective.   If  a filter  is  to be used between the
probe and the first impinger be sure that an acceptable stainless
steel mesh filter  support is packed; glass frit supports are not
acceptable.                                           / V 7

-------
                                             Section No.  3.9.3
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 2 of 6
Date        $~-//-S>O	  Calibrated by
Meter box number   F/3- /	  AH@ 	 /. S 7
Dry Gas Meter*

Pretest calibration factor Y    /. O/3         (within ±2% of the
  average factor for each calibration run).

Impinger Thermometer

Was a pretest temperature correction used?  	 yes     *x"_ no
  If yes, temperature correction  	r (within ±1°C (2°F)
  of reference values for calibration and within ±2°C (4°F) of
  reference value for calibration check)

Dry Gas Meter Thermometers

Was a pretest temperature correction made?  	 yes    *^    no
  If yes, temperature correction 	 (within ±3°C (5.4°F) of
  reference value for calibration and within 6°C (10.8°F) of
  reference values for calibration check)

Stack Temperature Sensor*

Was a stack temperature sensor calibrated against a reference
  thermometer?  	^"  	 yes  __^	^__ no
  If yes, give temperature range with which the readings agreed
  within ±1.5% of the reference values   3oo    to  36>o   K

Barometer

Was the pretest field barometer reading correct?   t^yes  	 no
  (within ±2.5 mm (0.1 in.) Hg of the mercury-in-glass barometer)

Nozzle*

Was the nozzle calibrated to the nearest 0.025 mm (0.001 in.)?
         yes  	 no
 *Most  significant items/parameters to be checked.
               Figure  3.1.  Pretest  sampling checks
o
                                                                       O
                                                           'i)C

-------
                                             Section No. 3.9.3
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 3 of 6
3.1.4   Pump - The vacuum pump  should be serviced as recommended
by   the manufacturer,   or every  3 mo, or  upon erratic behavior
(nonuniform or  insufficient pumping  action).   Check  the oiler
jars, if used, every 10 tests.
3.1.5   Dry Gas Meter  - A dry  gas  meter calibration check should
be made using  the procedure  in  Section 3.4.2.
3.1.6   Silica Gel  - Either  dry  the  used  silica  gel  at 175°C
(347°F)  for at least  2 h or use fresh silica gel.  Weigh  several
200-  to 300-g portions  in  airtight  containers  to  the  nearest
0.5 g if the  moisture  content is to  be  determined.   Record the
total  weight  (silica  gel plus  container)  for  each container.
3.1.7   Thermometers -  The thermometers  should  be  compared  to a
mercury-in-glass  reference  thermometer  at  ambient temperature.
3.1.8   Barometer  -  The field barometer should be compared before
each  field  trip  with  a mercury -in -glass  barometer or  with a
weather  station  reading  after  making an elevation  correction.
3-2  Reagents  and Equipment
3.2.1   Filters - Check  the  filters  visually against  light for
irregularities, flaws,  and pinhole leaks.  Determine the  F-blank
value by  analyzing three filters  chosen from each lot (Section
3.9.5);   if the value  is <_0.015 mg F/cm2  they are acceptable for
field use.
3.2.2  Water  - 100  ml  of deionized distilled water is needed for
each of the first two impingers and for sample recovery.
3.2.3   Ice - Crushed  ice  is needed  to  keep the gas  that exits
into the last  impinger below 21°C (70°F).
3.2.4   Stopcock grease  -  Silicone  grease that is  acetone  insol-
uble  and heat stable  may be  used sparingly at  each connection
point of the sampling train to prevent gas leaks;  but this is not
necessary if screw-on connectors with Teflon (or similar)  sleeves
are used.
3.3  Equipment Packing
     The accessibility, condition, and functioning of measurement
devices   in the  field  depend  on  careful  packing and  on  careful

-------
                                             Section No.  3.9.3
                                             Revision No.  0
                                             Date January 4,  1982     C  J
                                             Page 4 of 6

movement on site.  Equipment should be packed to withstand severe
treatment  during shipping  and  field  handling  operations.   One
major consideration  in shipping cases is  the  construction mate-
rials.   The  following containers  are  suggested, but are  not
mandatory.
3.3.1  Probe  - Seal  the inlet and outlet of the probe to protect
the probe  from breakage.   Pack the probe inside a container that
is  lined with polyethylene  or  other  suitable material  that is
rigid enough  to  prevent bending or twisting  during shipping and
handling; an ideal container is a wooden case (or the equivalent)
with  a  separate  compartment  lined with foam material  for each
probe, and should have handles  or eye-hooks .that can withstand
hoisting.
3.3.2    Impingers, Connectors,  and Assorted Glassware  -  All   im-
pingers  and  glassware should be  packed  in rigid  containers and     (  J
protected by polyethylene or other suitable material.   Individual
compartments  will help  to organize  and  protect  each  piece of
glassware.
3.3.3   Volumetric Glassware  - A  sturdy  case   lined  with  foam
material  is  suggested for  drying tubes and  assorted volumetric
glassware.
3.3.4  Meter Box  - The meter  box—which  contains the manometers,
orifice  meter, vacuum gauge,  pump, dry  gas .meter/  and thermom-
eters—should be  packed in  a  shipping container unless its hous-
ing is sufficiently  protective  for the components during travel.
Additional pump  oil  should be packed if oil  is  required.   It is
advisable to carry a spare meter box in case of failure.
3.3.5   Wash Bottles  and  Storage Containers - Storage  containers
and miscellaneous glassware  should  be  packed  in "a  rigid foam-
lined container.
                                                                      o
                                                     1'

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                                                      Section No.  3.9.3
                                                      Revision No.  0
                                                      Date January 4, 1982
                                                      Page 5  of 6
             TABLE 3.1  ACTIVITY MATRIX FOR  PRESAMPLING OPERATIONS
Apparatus
Sampling train
  probe and
  nozzle
Impingers,
  filter
  holders, and
  glass con-
  nectors
Pump
Dry gas meter
Acceptance limits
1.  Probe, nozzle, and
liner free of contami-
nants; constructed of
borosilicate glass,
quartz, or equivalent;
metal liner must be
approved by admini-
strator

2.  Probe leak free
at 380 mm (15 in.) Hg

3.  Probe heating
system prevents mois-
ture condensation
Clean; free of breaks,
cracks, leaks, etc.
Sampling rate of 0.02-
0.03 mVmin (0.7 to
1.1 fts/min) up to 380
mm (15 in.) Hg at pump
inlet
Clean; readings ±2% of
of average calibration
factor
Frequency and method
   of measurements
1.  Clean internally
by brushing with tap
water, deionized dis-
tilled water, and
acetone; air dry
before test
                                          2.   Check  using  pro-
                                          cedures  in Subsec 2.3

                                          3.   Check  heating
                                          system  initially and
                                          when moisture  cannot
                                          be  prevented during
                                          testing  (Sec 3.4.1)
Clean with detergent,
tap water, and
deionized distilled
water
Service every 3 mo
or upon erratic be-
havior; check
oiler jars every 10
tests
Calibrate according
to Sec 3.4.2; check
for excess oil
Action if
requirements
are not met
1.   Repeat
cleaning and
assembly pro-
cedures
                       2.   Replace
                       3.   Repair or
                       replace
Repair or
discard
Repair or re-
turn to manu-
facturer
As above
(continued)
                                                          v..

-------
                                                     Section No. 3.9.3
                                                     Revision  No. 0
                                                     Date January 4,  1982
                                                     Page 6 of 6
Table 3.1 (continued)
                                                                 o
Apparatus
Reagents and
  Equipment

Filters
Water
Stopcock grease
Packing Equip-
  ment for
  Shipment

Probe
Impingers, con-
  nectors, and
  assorted
  glassware
Pump
Meter box
Wash bottles
  and storage
  containers
Acceptance limits
No irregularities,
flaws, pinhole leaks;
<0.015 mgF/cm2
Deionized distilled
conforming to
ASTM-D1193-74,  Type 3
Acetone insoluble;
heat stable
Rigid container lined
with polyethylene foam
Rigid container lined
with polyethylene foam
Sturdy case lined with
polyethylene foam ma-
terial if not part of
meter box
Meter box case and/or
additional material  to
protect'train compon-
ents; pack spare meter
box
Rigid foam-lined con-
tainer
Frequency and method
   of measurements
Visually check before
testing; check each
lot of filters for F
content
Run blank evapora-
tions before field
use to eliminate high
solids (only required
if impinger contents
to be analyzed)
Check label
receipt
upon
Prior to each ship-
ment
As above
As above
As above
As above
           Action  if
           requirements
           are  not met
           Replace
           Redistill
           replace
                                                                          or
Replace
                                                                                  O
           Repack
           As above
           As above
           As above
           As above
                                                                                  O

-------
                                             Section No. 3.9.4
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 1 of 21
4.0  ON-SITE MEASUREMENTS
     The on-site activities include transporting equipment to the
test  site,  unpacking  and  assembling the equipment,  making duct
measurements,  performing   the  velocity  traverse,   determining
molecular weights  and stack  gas  moisture  contents,  sampling for
fluorides, and recording the  data.   Table 4.1 at the end of this
section  summarizes  the quality  assurance  activities  for on-site
activities.  Blank forms to be used in recording data are in Sec-
tion 3.4.12 for the convenience of the Handbook user.
4.1  Handling of Equipment
     The  most  efficient  means   of  transporting  or moving  the
equipment from  ground level  to  the  sampling  site  should be de-
cided  during the  preliminary  site  visit  (or prior correspon-
dence).   Care  should be exercised to prevent  damage  to the test
equipment or injury to test personnel during the moving phase.  A
"laboratory"  area  should be  designated for assembling  the sam-
pling  train,  placing the filter  in  the filter holder,  charging
the  impingers,  recovering  the sample,   and documenting  the  re-
sults; this  area should be  clean and  free  of excessive drafts.
4.2  Sampling
     The  on-site  sampling  includes preliminary measurements  and
setup, placing  the  filter  in the filter holder,  setting up the
sampling train,  preparing the probe,  checking for leaks along the
entire train,  inserting the  probe  into the  stack,  sealing the
port,  checking  the  temperature of the  probe,  sampling at desig-
nated  points,  and recording  the  data.   A  final  leak check must
always be performed upon completion of the sampling.
4.2.1   Preliminary Site Measurements  - These  measurements  are
needed  for  locating  the  pitot   tube  and  the probe during  the
sampling.
     1.   Be sure the site meets Method 1 specifications; if not,
due  to duct  configuration  or other- reasons,  have the  site  ap-
proved by the administrator.
                                                        'ft

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                                             Section No.  3.9.4
                                             Revision No.  0
                                             Date January 4,  1982      x—s
                                             Page 2 of 21             I)

     2.   Be  sure  a 115-V,  30-A electrical supply  is  available
for operating the standard sampling train.
     3.   Either  measure  the stack  and  determine  the  minimum
number  of traverse  points  by Method  1,  or  check  the  traverse
points  determined  during the  preliminary  site visit  (Section
3.0).
     4.   Record all data on the  traverse  point location  form
shown in Method 1.   These measurements will be used to locate the
pitot tube and the sampling probe during preliminary measurements
and actual sampling.
The  site  must be  accepted before  a valid sample can be  taken.
4.2.2   Stack  Parameters  - By the  following preliminary  measure-
ments,  the  user  can  set  up  the  nomograph  as  outlined  in
APTD-0576.4  An example nomograph data form is Figure 4.1.   Using
the  stack parameters obtained,   the isokinetic  sampling  rate can
be set.
     1.   Check the sampling site for cylonic or nonparallel flow
(Method 1, Section 3.0).
     2.   Determine  the  stack   pressure,  temperature,  and  the        ';
range of velocity heads encountered (Method 2).
     3.   Calculate  the  moisture  content by  using  Method  4 or
its  alternatives.   If  the source has been tested  before  or  if a
good  estimate of  the  moisture  is  available,  this  value  can be
used  to avoid calculations.   If the stack gas  is  saturated with
moisture  or  has  water  droplets,  the  moisture  content must be
determined  by using stack  gas  temperature  sensor  (Method 4).
     4.   Calculate  the dry  molecular  weight  (M,)  of the stack
gas  (Method 2).   If an integrated gas sample is required,  follow
Method  3  procedures and  take the  gas  sample simultaneously with
and  for the  same  total length  of  time as the  fluoride sample.
     5.   Record the data on the sampling and the analytical data
forms  for molecular weight determinations located in Section 3.2,     [)
Method 3.                                                            ^-^
Note;   The  condensate  collected during  the  sampling can be  used
in  the final calculations  of moisture  content  (Section 3.9.6).   ,   
-------
                                             Section No.  3.9.4
                                             Revision No.  0
                                             Date January 4,  1982
                                             Page 3  of 21
Plant
Date
Sampling location
 Calibrated pressure differential across
   orifice, in. H2O
 Average meter temperature (ambient + 20°F),  °F
 Percent moisture in gas stream by volume,  %
 Barometric pressure at meter,  in. Hg
 Static pressure in stack,  in.  Hg
   (Pm±0.073 * stack gauge pressure,  in.  H2
 Ratio of static pressure to meter pressure
 Average stack temperature,  °F
 Average velocity head,  in.  H2O
 Maximum velocity head,  in.  H2O
 C factor
 Calculated nozzle diameter, in
 Actual nozzle diameter,  in.
 Reference Ap, in. H2O
                                                   m
                                                    avg

 wo
  avg
AP
  avg
          SO
                                                         a 1.
       - O-OI
         0-3
         /.
       0.38S
       0. 37S
        0-148
        Figure 4.1.  Nomograph data form (English units).

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                                             Section No. 3.9.4
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 4 of 21

4.2.3  Sampling Rate  -  Method  13  sampling is performed isokinet-
                                                            3
ically like- Method  5,  but the sampling rate must be <0.03 m /mm
       3
(1.0 ft /min) during the test; the maximum AH will limit the rate
to <0.03 m3/min (1.0 ft3/min).
     1.   Select  a  nozzle  size  based  on the range  of velocity
heads, so  that the nozzle  size  will not have to be  changed to
maintain an isokinetic sampling rate.
     2.   Select a nozzle that will maintain the maximum sampling
               3            3
rate at <0.03 m /min  (1.0 ft /min) during the run.
     3.   Check  the  maximum  AH,   using the  following equation:
                   1.09 P  M AH@
     Maximum AH <_  - = -                     Equation 4-1
                           m
where
     Maximum AH = pressure differential across the orifice that
                  produces a flow of 1.0 ft /min, in. H20;
             P  = pressure of the dry gas meter, in. Hg;
              M = molecular weight of the stack gas;
            AH@ = pressure differential across the orifice that
                  produces a flow rate of 0.75 scfm, in. H20; and
           .  T  = temperature of the meter, °R.
     4.   Install  the  selected nozzle using  a Viton A 0-ring if
glass or stainless steel liners are used; install the nozzle on a
stainless steel  liner  by using a leak-free mechanical connection
(APTD-05764) or Teflon ferrules.
     5.   Mark the probe with heat resistant  tape or with another
acceptable means to denote the proper distance to which it should
be inserted into the stack or duct at each sampling point.
     6.   Select  a total sampling time  that  is  greater  than or
equal  to  the minimum  total  sampling time  specified in the test     /"""N
procedures for the specific industry so that —                        ^ — ^
          a.   The  sampling  time  per  traverse point  is >2 min
(greater  time interval  may  be specified  by  the administrator);  .— y/(-
                                                                      '

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                                             Section No. 3.9.4
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 5 of 21

the number of  minutes  sampled at each point is either an integer
or  an  integer  plus one-half  minute  to  avoid timekeeping errors.
          b.    The sample volume corrected to standard conditions
exceeds  the  required  minimum  total gas  sample  volume  (can  be
based on  an  approximate  average sampling rate).  In some circum-
stances  (e.g.,  batch cycles), it may be  necessary to sample for
shorter times  and to  obtain  smaller gas  sample  volumes;  if so,
obtain the administrator's approval.
     7.   Record the data on the fluoride field data form (Figure
4.2).
4..2.4   Sampling Train  Preparation  - These  steps  are  needed for
preparing the sampling train.
     1.   Keep all openings where contamination can occur covered
until  just before assembly of the setup  or before beginning the
sampling.
     2.   Place  100  ml of distilled water (a graduated cylinder
may be used)  in each of the first two impingers.
     3.   Leave the third impinger empty.
     4.   Add  200-300  g  of preweighed  silica gel  in  the fourth
impinger  and place the empty container in. a  safe place for use
later in the sample recovery, and record the weight of the silica
gel and the  container  on the appropriate data form.  If moisture
content is to  be determined by  impinger  analysis,  weigh each of
the first three  impingers  to the nearest 0.5 g, and record these
weights.
     5.   Use  tweezers or  clean  disposable surgical  gloves  to
place the filter in the filter holder.
     6.   Be sure  that the filter is properly centered and that
the gasket is  properly placed  to  prevent  the  sample gas stream
from circumventing the filter.
4.2.5   Sampling Train  Assemblage - The  arrangement of  .the sam-
pling train components is shown in Figure 1.1.
     1.   Apply  if needed to avoid contamination a  very  light
coat of  silicone grease,  but only on the  outside of all ground-
glass joints.                                               '      /t'l//

-------
Plant
              faicr
Locatio
Operator
Date .T~
           ~ fiO
Run number 	
Stack diam, xz
Meter calibration (Y) _
Pi tot tube (C )  f).f}4
Probe length p//? x/
Probe liner material  ^
Probe heater setting  ^
Ambient temperature
       Sheet
       Nozzle
                                                                                                of
                                                                                     identification
                                                                              Nozzle diameter ft
                                                                              Thermometer number
                                                                              Final  leak rate
                                                                                                      7_
                                                                                                    number
                                                                                                       mm (in.
                     7/9,3
Sample box nuraber
Heter box number •:
Meter AH9
Barometric pressure (•.
Assumed moisture  ^""
Static pressure (
C Factor  /?O£,
                                                                -

                                                                                                                   cn^
                              £L
                                                 Q.39
                                                                                    &L.
                                                                       £V_
                                                                                      < o
                                                                                      H-d-
                                                                                      tn H-
                                                                                      H-O
                                                                                      O J3
                                                                                                       37
                            3.5-
                                       3/3
                                                                                     61
                                                                                             •57
                                                                                    6/
                                                                            -793
                                                                                                       (Ft
                                                                                                                       O •


                                                                                                                       O •
                                                                                                                         \0
                            3.0
                                                 n.zn
                                                            /.
          Total
                                                                       Total
                                                                                                     Hax
                                  Figure 4.2.   Fluoride field data form.
                                                                                                                    vo
                                                                                                                    oo
                                                                                                                    ro
        O
                                                            o
                                                                                                                 o

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                                             Section No. 3.9.4
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 7 of 21

     2.   Either place the filter immediately following the probe
or between  the third and  fourth  impingers.   Normally the filter
will be  placed  after  the third  impinger unless  the filterable
particulate fluoride  is  to be measured.   It  is  not necessary to
have filters in both positions.  If in the front filter position,
use  a  20-mesh  stainless  steel filter  support  with   a silicone
outer seal.
     3.   Place crushed ice and water around the impingers.
     4.   Check the filter to be sure there are no tears.
     5.   Attach a temperature  sensor  to  the metal sheath of the
sampling  probe  if  it is  not  already  an integral part  of  the
assembly, so  that the  sensor  extends  beyond the  probe  tip  and
does not touch  any metal;  the  sensor should  be  about  1.9  to
2.54 cm  (0.75  to 1 in.)  from the pitot  tube and  the  nozzle to
avoid  interference  with  the  gas flow;  other  arrangements  are
shown in Method 2.
4.2.6  Sampling Train Leak Checks - Leak  checks  are necessary to
ensure that the  sample  has not been biased  low  by dilution air.
The Reference Method  (Section 3.9.10)  specifies  that leak checks
be performed at  certain  times as  discussed below.  Leakage rates
<4%  of  the  average  sampling  rate  or  0.00057  m3/min  (0.02
ft3/min), whichever is less,  are acceptable.
4.2.6.1  Pretest -  (optional) If the tester  opts  to  conduct the
pretest  leak check, the  following procedure  should be used after
the sampling train has been assembled.
     1.   Set the filter heating  system at the desired operating
temperature.
     2.   Allow the temperature to stabilize.
     3.   If a Viton  A  O-ring or other leak-free  gasket is  used
to connect  the probe nozzle  to the probe liner,  leak check the
train  at the  sampling site by plugging the nozzle  and pulling a
vacuum of 380 mm (15  in.)  Hg.  Note;   A lower vacuum may be used
if it is not exceeded during the test.
     4.   If an  asbestos string is  used for  the  probe gasket,  do
not connect the probe to the  train;  instead,  first plug the inlet

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                                             Section No.  3.9.4
                                             Revision No. 0
                                             Date January.4,  1982
                                             Page 8 of 21

to the filter holder and pull a vacuum of 380 mm (15 in.) Hg (see
previous note),  and then connect the probe to  the  train to  leak
check at a vacuum of about 25 mm  (1 in.) Hg.
     Alternatively,  the  probe may be leak  checked  with  the  rest
of the sampling  train  in one step at a vacuum of 380 mm (15 in. )
Hg (APTD-05813 and APTD-05764).
     1.   Start the pump with the bypass valve fully open and the
coarse adjust valve closed.
     2.   Open  the  coarse  adjust  valve,   and  slowly close  the
bypass valve  until  the desired vacuum is reached.  Note:  Do not
reverse the  direction  of the bypass valve; this  will cause  dis-
tilled  water  to back up  from the  impingers  into the  filter
holder.  If the  desired vacuum is exceeded, either leak check at
the higher vacuum  or end the leak check (step 3 below) and start
over.
     3.   When the leak check is complete,  slowly remove the plug
from  the  inlet  to  the probe  or  the  filter  holder; close  the
coarse adjust valve; and immediately turn off the vacuum pump to
prevent the impinger water from being forced back into the filter
holder and to prevent  the silica gel from being forced back into
the third impinger.
     4.   Visually  check to be  sure  that  water  did not contact
the filter and  that the filter has no tears before beginning the
test.
4.2.6.2   During the Sampling  -  If.  a  component  (e.g.,  filter
assembly or  impinger)  change is necessary  during the test,  con-
duct  a  leak  check  before  the change,  according  to the step-by-
step procedure outlined above.
     1.   Record the initial dry gas meter reading on Figure 4.2.
     2.   Be  sure  the  vacuum is  equal to or  greater  than  the
maximum value recorded up to that point in the test.
                                             3/            3
     3.   If  the  leakage rate  is  £0.00057  m  7min  (0.02 ft /min)
or  4% of  the  average  sampling rate  (whichever is  less),  the
results are  acceptable, so no correction need  be applied to the
total volume of dry gas metered.
o

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                                             Section No. 3.9.4
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 9 of 21

     4.   If a higher leakage rate is obtained, either record the
leakage  and correct  the  sample volume  (Section 6.3(b)  of  the
Reference Method, Section 3.9.10), or void the sample run.
     5.   Record  the  final dry gas meter reading on Figure 4.2.
4.2.6.3  Posttest - (mandatory)  At  the conclusion  of each sam-
pling run,  conduct a leak check in accordance with the procedures
above.
     1.   Record the initial dry gas meter reading on Figure 4.2.
     2.   Be sure the  vacuum  is equal  to  or greater  than  the
maximum recorded during the sampling run.
                                             3              3
     3.   If the  leakage rate is  <_0.00057  m /min (0.02 ft /min)
or  4% of  the  average  sampling  rate  (whichever is  less),  the
results are  acceptable, so no correction need be applied to the
total volume of dry gas metered.
     4.   If a higher leakage rate is obtained, either record the
leakage rate  and  correct  the  sample volume  (Section 6.3(a)  or
6.3(b)  of  the  Reference  Method,  Section  3.9.10),  or  void  the
sample run.
     5.   Record the dry gas meter reading on Figure 4.2.
4.2.7   Sampling Train Operation  -  Just  before  beginning  the
sampling,  clean the portholes  to minimize  the chance of sampling
any deposited  materials.  Verify that  the  probe  and  the filter
heating systems  (if required)  are up to the desired temperatures
and verify  that  the  pitot  tube  and the  nozzle  are  positioned
properly.   Follow the procedure below for sampling:
     1.   Record  the  initial dry gas meter readings,  barometric
pressure,  and other data on Figure 4.2.
     2.   Position  the  tip  of the probe  at  the first sampling
point with the  nozzle  tip  pointing directly into the gas stream.
When in position,  block off the open area  around the probe and
the porthole  to  prevent flow disturbances  and  unrepresentative
dilution of the gas stream.
     3.   Turn  on the  pump,  and immediately  adjust  the  sample
flow to attain isokinetic conditions;  maintain a sampling rate of
±10% of the  isokinetic  rate  (unless  otherwise specified  by  the

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                                             Section No.  3.9.4
                                             Revision No.  0
                                             Date January 4,  1982
                                             Page 10 of 21

administrator), and  adjust the rate  at any sampling  point  if a
20% variation  in  velocity  pressure occurs.   Note:  Do not exceed
the  maximum AH.   Use  nomographs or  programmed  calculators  to
rapidly determine the  orifice  pressure drop corresponding to the
isokinetic sampling  rate.   If  the nomograph is designed as shown
in APTD-0576,4  use  it only with  a Type  S pitot tube which has a
C  coefficient of 0.85 ±  0.02 and only when  the  stack  gas  dry
molecular weight  (M,)  is 29 ±  4,  if C_  and M_ are outside these
                                      P
limits, do  not use  the nomograph without  compensating  for  the
differences.   Recalibrate  the  isokinetic rate  or reset the nomo-
graph  if  the  absolute stack  temperature   (T  ) changes  by >10%.
                                             5
     4.   Take other required readings (Figure 4.2) at least once
at each sampling point during each time increment.
     5.   Record the final  dry gas meter readings (Figure 4.2) at       ^_^
the end of each time increment.                                        (   )
     6.   Repeat steps 3 through 5 for each sampling point.
     7.   Turn  off  the pump;  remove  the  probe  from  the stack;
record the final readings after each traverse.
     8.   Conduct  the  mandatory   posttest   leak  check  (Subsec-
tion 4.2.6.3) at the conclusion of the last traverse.  Record any
leakage rate.   Also,  leak check  the pitot  lines  (Method 2,  Sec-
tion 3.1.2); the  lines  must pass  this leak check to validate the
velocity pressure data.
     9    Disconnect the probe,  and then cap  the nozzle and the
end of the probe with polyethylene or equivalent caps.
     Periodically during the test,  observe  the connecting glass-
ware—from the probe, through the filter, to the first impinger—
for  water condensation.   If  any is  evident,  adjust the probe
and/or  filter  heater  setting  upward  until the  condensation  is
eliminated;   add  ice  around the impingers to maintain the silica
gel exit temperature at 20°c (68°F).
     The manometer level and zero should also be checked periodi-
cally during each traverse.  Vibrations and temperature fluctua-
tions can cause the manometer zero to shift.
o

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                                             Section No. 3.9.4
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 11 of 21

4.3  Sample Recovery
     After the sampling is complete and the data are recorded for
all points, begin the cleanup procedure immediately.
     1.   Allow the probe to cool until it can be safely handled.
     2.   Wipe off  all external particulate matter near the tip
of the probe nozzle.
     3.   Cap  the  tip  loosely to keep  from losing part  of the
sample; capping  it tightly while  the sampling train  is cooling
can cause  a vacuum to  form in the filter holder,  and can cause
impinger water to.be drawn backward.
     4.   Remove the  probe from  the  sample train  before  moving
the sample train to the cleanup site.
     5.   Wipe off  the silicone grease,  and cap  the open outlet
of  the probe;  be  careful  not to  lose  any  condensate that  is
present.
     6.   Wipe off  the  silicone  grease  from  the  filter  holder
inlet, and cap this inlet.
     7.   Remove the  umbilical cord  from the last impinger and
cap the impinger.
     8.   Wipe  off the  silicone  grease and  then  cap off the
filter holder outlet and any open impinger inlets or outlets with
ground-glass stoppers, plastic caps,  or serum caps.
     9.   Transfer the probe  and  the  filter-impinger assembly to
an area that is clean and protected from the wind to minimize the
chances of contaminating or  losing  any of the  sample.  Inspect
the train  before and  during  disassembly, and note any abnormal
conditions.
4.3.1   Probe,  Filter, and Impinqer Catches  -  This step-by-step
procedure  should be followed  carefully  to  recover virtually all
of the sample collected in the probe,  filter, and impinger.
     1.   Use  a  graduated  cylinder  to  measure  (to the nearest
1 ml)  the  volume of  water  in the first three  impingers and any
condensate in the probe.
     2.   Record the  values on the sample recovery and integrity
form Figure 4.3.

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                                              Section No. 3.9.4
                                              Revision No. 0
                                              Date January 4, 1982
                                              Page 12 of 21
Plant   Q-SxiTvv>L™jLL^vO  SvwJI±Ln,   Sample date T^O-u 7.
                                                      sj  J
Sample location     P
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                                             Section No. 3.9.4
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 13 of 21

     3.   Transfer the impinger water from the graduated cylinder
into a polyethylene container.
     4.   Add  the  filter  to  this   container  using  procedures
subject to the Administrator's approval.
     5.   Be sure that  dust on the outside of the probe or other
component  (e.g.,  the probe nozzle,  probe  fitting,  probe liner,
first  three  impingers,   impinger  connectors, and  filter holder)
does not get into  the sample while cleaning other sample-exposed
surfaces with  deionized distilled water;  use  <500 ml  for  the
entire  wash,  and  add  these, washings  to  the  washings  and  the
filter in the polyethylene  container.  To this container add the
rinsings from the probe and nozzle, as described in the following
procedure.
     Probe and Probe Nozzle  -  Having  two people  clean the probe
should minimize sample  losses.   Keep  brushes clean and protected
from contamination at all times.
     1.   Carefully remove,  the probe  nozzle,  use a Nylon bristle
brush  to loosen  particles  from  the  inside  surfaces;  use a wash
bottle to rinse with deionized distilled water until no particles
are visible.
     2.   Brush and  rinse the inside parts  of  the Swagelok fit-
ting with deionized distilled water in a similar way.
     3.   Rinse the probe liner  by squirting deionized distilled
water into the upper end of the probe and by tilting and rotating
the probe  so that  all  inside surfaces  are wetted, and  let  the
water  drain from  the lower  end through  a  funnel  (glass or poly-
ethylene) and into the container.
     4.   Follow the  rinse  with a cleaning with  a  probe brush.
Hold  the probe  in  an  inclined position,  and  sguirt deionized
distilled water into the upper end while pushing the brush with a
twisting action  through the probe  and  catching  any  water  and
particulate matter that is brushed from the probe into the sample
container.   Note:   Brush three times, or at  least six times  for
stainless steel or  other probes which  have  small  crevices that
entrap particulate matter.

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Section No. 3.9.4
Revision No. 0
Date January 4, 1982
Page 14 of 21
                                                                     o
                          o
     5.    Rinse  the brush  with  deionized  distilled water,  and
quantitatively  collect these  washings  in the  sample container.
     6.    After  cleaning  the  brush,  make a  final rinse  of the
probe by repeating steps 1-3.
     Impinger and Filter Assembly - To  recover  fine particulates
from these  components, brush,  wash,  and  add  the  rinsings  to the
container.
     1.    Rinse  the inside  surface  of  each  of  the  first three
impingers and their connecting glassware three  times using small
portions  of deionized distilled water  for each rinse,  and brush
each sample-exposed surface with a Nylon bristle brush,  to ensure
recovery  of fine particulate matter.   Make a final rinse of each
surface and the brush.
     2.    Be sure  that all  joints have been wiped clean of sili-
cone grease before brushing and rinsing with deionized distilled
water the inside of the filter holder  (front-half only if after
the  third impinger) three or more times  as needed;  make a final
rinse of the brush  and filter holder.                              ;
     Container  - The following steps should be followed after all
water washings  and particulate matter have been collected in the
sample container.
     1.   Tighten  the  lid so that water will not leak out when it
is shipped  to the  laboratory.
     2.   Mark  the height  of the  fluid level  so that the re-
ceivers can determine  whether leakage has occurred during trans-
port.
     3.   Label the container clearly  to identify its contents;
example sample  label is shown  in Figure 4.4.
4.3.2  Sample Blank -  Prepare  a blank by placing  an unused filter
in a polyethylene  container  and by adding a volume of water equal
to the  total volume in the  average sample.  Process the blank in
the  same  manner as  the field samples.                                  C   j
4.3.3   Silica Gel - Note the  color  of the indicating silica gel
to  determine whether  it has  been  completely  spent, and  make  a
notation  of its condition on Figure 4.3.                             ' /\
                                                                    • I  -
                                                                    v / -

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                               Section No. 3.9.4
                               Revision No. 0
                               Date January 4, 1982
                               Page 15 of 21
Plant Alu/niwm 5/wt.rtA City C a past ^/fu, 77/vtf-
II //
Site S'we.rM Our<.er Sample type P/uoAiJt SAtnple
Date /--^-go Run number AS-J*
Front rinse G' Front filter S' Front solution D
Back rinse 0^ Back filter B' Back solution C3X
Solution Level marked
• •
Volume: Initial Final ^
	 — s-
Clean up by §
— ... , ^



































Figure 4.4.   Example of a sample label.

-------
                                             Section No. 3.9.4
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 16 of 21
     1.   Transfer the silica gel from the fourth impinger to its
original  container  using  a  funnel  and  a rubber  policeman,  and
seal  the  container.   It is not necessary  to  remove the  small
amount of dust particles  that  may adhere to the  impinger wall;
since  the weight gain is used  for moisture  calculations,  do not
use water or other liquids to transfer the silica gel.
     2.   Determine the  final  weight gain to the  nearest 0.5 g>
if a balance is available.
4.4  Sample Logistics  (Data) and Packing of Equipment
     Follow  the  sample  recovery procedures  for the  required
number of test runs,  and record all data  on Figure 4.3.   If the
probe  and the glassware  (impinger, filter holder, and connectors)
are to be used in the next test, rinse all with distilled deion-
ized water and then acetone.  To document the data and to prepare
the sample for shipping the following steps are recommended after
the test.
     1.   Check all sample containers  for proper labeling (time,
date,  and location of  tests,   number  of tests,  and any other
pertinent  data)..   Be  sure a blank  has  been taken and  labeled.
     2.   Duplicate all  data recorded during the  field  test, to
avoid  costly mistakes, by using  either carbon paper or data forms
and a  field laboratory notebook.  Avoid using water soluble pens.
     3.   Mail one  set of data to the base laboratory or give it
to  another team member  or to personnel  in the  agency; handcarry
the other  set.
     4.   Examine  all sample  and blank  containers and  sampling
equipment for  damage and  for proper packing for shipment to the
base  laboratory,  and  label all  shipping containers  to prevent
loss of samples or  equipment.
     5.   Make  quick  checks  of  sampling  and  sample  recovery
procedures by using the  on-site  checklist, Figure  4.5.
o
 o
 o

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                                           Section No. 3.9.4
                                           Revision No. 0
                                           Date January 4, 1982
                                           Page 17 of 21
Apparatus

Probe nozzle:  stainless steel 	>s 	  glass
  Button-hook     \^	 elbow 	  size
  Clean?
Probe liner:  borosilicate	  quartz 	  other
  Clean?
  Heating system*
  Checked?
Pitot tube:  Type S  	ix- .	  other
  Properly attached to probe?*	
  Modifications
  Pitot tube coefficient
Differential pressure gauge:  two inclined manometers
  other _ ^       sensitivity  p.Ot -    o to /
Filter holder:  borosilicate glass    ^ _ glass frit
  filter support _  silicone gasket _  other
  Clean?      yS
               _
Condenser :  number of impingers
  Clean?
  Contents   1st /G£>/rjj #
-------
                                            Section No.  3.9.4
                                            Revision No.  0
                                            Date January 4,  1982
                                            Page 18 of 21
-Figure 4.5  (continued)
Meter box  leveled?      />JL^	  Periodically?
Manometers  zeroed?
AH@  from most  recent  calibration    /.
Nomograph  setup properly?
Care taken  to .avoid  scraping nipple  or stack wall?*
Effective seal  around  probe  when in-stack?
Probe moved at  proper  time?
Nozzle  and pitot  tube  parallel  to stack wall at all times?*
  Filter changed  during run?
  Any particulate lost?   -T^LA
Data  forms  complete  and data  properly recorded?*  _     	  	 _
Nomograph setting  changed when stack temp changed significantly?
Velocity pressure  and  orifice  pressure readings recorded
  accurately?*
Sampling performed  at a  rate  <1.0  cfm?        	
Posttest leak  check performed?*      LU^>   u	 (mandatory)
Leakage rate    o. o/	 @ in.  Hg   /S" .w,..  	
  Orsat analysis     AXXI^   from stack 	 integrated    ^          ^^^
  Fyrite combustion Analysis  	  sample location 	       I)
  Bag system leakchecked?*    u^u^>	       V	/
  If data  forms cannot be  copied,  record:
    approximate stack temp  31 7e>f     volume metered   81
    % isokinetic  calculated  at end of each run 	

SAMPLE RECOVERY

Brushes:   nylon bristle    (AJU^>	  other
  Clean?    /
Wash bottles;" polyethylene  or glass
  Clean?
Storage containers:polyethylene   -^_;	
Probe allowed  to  cool  sufficiently?      /^o-. <^X? 5"..	
Cap placed over nozzle tip  to prevent loss of particulate?*
During sampling train  disassembly,  are all openings capped?
Clean-up area  description:
  Clean?          iM^*             Protected from wind?
          _    _
Filters:  paper   ° jue^^>       ~ _  type
  Silica gel:  type" (6  to  16  mesh)?   new?   ^iJL^-J  used?
  Color?    ^JjJLuut ^ _ Condition?Q   Ci
Filter handling:   tweezers used?
  surgical  gloves?   _        other
  Any  fluoride  spilled?*
 (continued)                                                         )/

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                                           Section No.  3.9.4
                                           Revision No. 0
                                           Date January 4,  1982
                                           Page 19 of 21
Figure 4.5 (continued)

Water distilled?        	
Stopcock grease:  acetone-insoluble?
  heat-stable silicone?  	^
Probe handling:  distilled water rinse
Fluoride recovery from:  probe nozzle    ^  	
  probe fitting    uu^	  probe liner
                                          (/other
  front half of filter holder
Blank:  filter
                                     distilled water
Any visible particles on filter holder inside probe?:*
All jars adequately labeled?  _
  Liquid level marked on jars?*
  Locked up?	
Filter blank
                                        Sealed tightly?
                0
*Most significant items/parameters to be checked.

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                                                     Section No.  3.9.4
                                                     Revision No. 0
                                                     Date  January 4,  1982
                                                     Page  20 of 21
                                                                  o
           TABLE 4.1.   ACTIVITY MATRIX FOR ON-SITE MEASUREMENT CHECKS
Apparatus
Sampling

Filter
Condenser
  (addition of
  reagents)
Assembling
  sampling
  train
Sampling
  (isokineti-
  cally)
Acceptance limits
Centered in holder;  no
breaks, damage,  or con-
tamination during
loading
100 ml of distilled
water in first two
impingers; 200-300 g
silica gel in fourth
impinger
of
1.  Specifications
in Fig 1.1
                 2.   Leak  rate <4% of
                 sampling  volume or
                 0.00057 mVmin (0.02
                 ftVmin), whichever is
                 less
1.   Within ±10% of
isokinetic condition
and at a rate of less
than 1.0 ftVmin

2.   Standard checked
for minimum sampling
time and volume; sam-
pling time >2 min/pt
    Frequency and method
       of measurements
    Use tweezers  or surg-
    ical  gloves  to  load
Use graduated cylinder
to add water, or weigh
each impinger and its
contents to the near-
est 0.5 g
    1.   Check specifica-
    tions before each
    sampling run

    2.   Leak check before
    sampling by plugging
    nozzle or inlet to
    first impinger and
    pulling a vacuum of
    380 nnn (15 in.) Hg
    1.   Calculate for
    each sample run
                                         2.  Make a quick cal-
                                         culation before test,
                                         and exact calculation
                                         after
                       Action if
                       requirements
                       are  not met
                       Discard fil-
                       ter, and
                       reload
                           Reassemble
                           system
                                                                                   O
                       1.
                       ble
                                               2.
                                               the
Reassem-
                          Correct
                          leak
                       1.   Repeat
                       the  test run
                          2.  As above
(continued)
                                                                                   O

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                                                     Section  No. 3.9.4
                                                     Revision No.  0
                                                     Date January  4,  1982
                                                     Page 21  of 21
TABLE 4.1 (continued)
Apparatus
Sample recovery
Sample
  logistics,
  data collec-
  tion, and
  packing of
  equipment
Acceptance limits
                 3.   Minimum  number of
                 points  specified  by
                 Method  1
                 4.   Leakage  rate
                 <0.00057 mvmin (0.02
                 ftVmin) or  4% of  the
                 average sampling vol-
                 ume,  whichever is  less
Noncontaminated sample
1.  All data recorded
correctly
                 2.   All  equipment exam-
                 ined for damage  and
                 labeled  for shipment
                 3.   All  sample contain-
                 ers and blanks properly
                 labeled and packaged
Frequency and method
   of measurements
                         3.   Check  before the
                         first  test run by mea-
                         suring duct and using
                         Method 1
                         4.   Leak check  after
                         each test run or be-
                         fore equipment  re-
                         placement during test
                         at  the  maximum  vacuum
                         during  the test (man-
                         datory)
Transfer sample to
labeled polyethylene
container after each
test run; mark level
of solution in the
container
1.   After each test
and before packing
                         2.   As  above
                         3.   Visually check
                         after each  sampling
Action if
requirements
are not met
                       3.   Repeat
                       the  procedure
                       to comply
                       with specifi-
                       cations  of
                       Method  1

                       4.   Correct
                       the  sample
                       volume  or re-
                       peat the sam-
                       pling
Repeat the
sampling
1.  Complete
the data
                       2.   Repeat
                       the sampling
                       if  damage
                       occurred ...dur-
                       ing the  test

                       3.   Correct
                       when possible

-------
o
o
o

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                                             Section No. 3.9.5
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 1 of 19
5.0  POSTSAMPLING OPERATIONS
     The postsampling operations  include  checks on the apparatus
used in  the field during  sampling to measure  volumes,  tempera-
tures,  and  pressures,  and  analyses  of the  samples  collected in
the field and forwarded to the base laboratory.  Table 5.1 at the
end of  this section summarizes  the  quality assurance activities
for the postsampling operations.
5.1  Apparatus Checks
     Posttest checks will have to be made on most of the sampling
apparatus.  These checks will include three calibration runs at a
single  orifice  meter setting;  cleaning; and/or  routine mainte-
nance. .   Cleaning  and maintenance  are  discussed in Section 3.4.7
and in APTD-0576.4  Figure 5.1 should be used to record data from
the posttest checks.
5.1.1  Metering System  - The metering system  has two components
that must be checked-r-the  dry .gas meter  and the dry  gas meter
thermometer(s).
     The dry gas  meter  thermometer(s)  should be compared with an
ASTM mercury-in-glass thermometer at room  temperature.   If the
two readings  agree  within ±6°C  (10.8°F),  the meter  reading is
acceptable;  if  not, the  meter thermometer  must  be  recalibrated
(Subsection 2.2,  Section  3.4.2) after the  posttest  check of the
dry gas  meter.   Use the higher  meter  thermometer reading (field
or  recalibration  value)  in  the  calculations.   If  the  field
readings  are  higher than  the  recalibration reading,  no tempera-
ture  correction  is necessary;   if  the  recalibration  value  is
higher,  add the difference in the two readings to the average dry
gas meter temperature reading.
     The posttest check of the dry gas meter is described in Sec-
tion 3.4.2.  Any  leaks  in  the  metering system should  have been
corrected before  the posttest check.   If the dry gas meter cali-
bration  factor  (Y)  deviates by  <_5%  from the initial calibration
factor,   the meter  volumes obtained  during the  test  series are
                                                       /•''" , *\f~> I
                                                      '/A^

-------
                                             Section No. 3.9.5
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 2 of 19
                                                                       o
Plant  RlumiNUff)  Smeller  Calibrated by     "7T  /
Meter box number  FB'I	  Date    4/- 3/...-.8O.

Dry Gas Meter
Pretest calibration factor, Y    /D. Q86>	  •      (within ±2%)
Posttest check, Y*  . Q.38'7	 (within ±5% of pretest)
Recalibration required?  	 yes  	>S"         no
  If yes, recalibration factor, Y 	       (within ±2%)
Lower calibration factor, Y  &.4£6>  for calculations (pretest or
  posttest)

Dry Gas Meter Thermometers

Was a pretest temperature correction used?  _^____ yes    *s*   no
  If yes, temperature correction 	 (within ±3°C (5.4°F) over
  range)
Posttest comparison with mercury-in-glass thermometer?* (within
  ±6°C (10.8°F) at ambient temperature)
Recalibration required?  	|	 yes  	\s*        no       .—^
Recalibration temperature correction?""             (within ±3°C      C   ]
  (5.4°F) over range)*                                                 v~x
  If yes, no correction necessary for calculations if meter
  thermometer temperature is higher; if calibration temperature
  is higher, add correction to average meter temperature for
  calculations

Stack Temperature Sensor

Was a pretest temperature correction used?  	 yes    */* •  no
  If yes, temperature correction 	°C  (°F) (within ±1.5% of
  readings in K (°R) over range)
Average stack temperature of compliance test, T     78O    K
Temperature of reference thermometer or solution for recalibre
  tion   £-£$    K (@)* (within ±10% of T )
Temperature of stack thermometer for recalibration  S"<28   K
Difference between reference and stack thermometer temperaturesT"'
  AT   '  o    K (°R)
Do values agree within ±1.5%?*  	t^     yes  	 no
  If yes, no correction necessary for calculations
  If no, calculations must be done  twice—once with the recorded
  values and once with the average  stack temperature corrected to
  correspond to the reference temperature differential (AT  ),
  both final result values must be  reported  since there is no way
  to determine which is correct                                        /^~\


            Figure 5;1  Posttest calibration checks.

 (continued)                                                 ^<

-------
                                             Section No. 3.9.5
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 3 of 19
Figure 5.1  (continued)

Barometer

Was the pretest field barometer reading correct?   tx"" yes _ no
Posttest comparison?* ^9. £-£" mm  (in.) Hg  (±2.5 mm  (0.1 in.) Hg)
Was calibration required?  _ _____ Yes           ^     no
                           _ _____      _
  If yes, no correction necessary for calculations when the  field
  barometer has a lower reading; if the mercury-in-glass reading
  is lower, subtract the difference from the  field data readings
  for the calculation
*Most significant items/parameters to be checked.

-------
o
                                             Section No.  3.9.5
                                             Revision No.  0
                                             Date January 4,  1982
                                             Page 4 of 19

acceptable; if Y deviates by >5%,  recalibrate the. metering system
(Section 3.9.2).  In the calculations,  use the calibration factor
(initial or  recalibration)  that yields the  lower  gas  volume for
each test run.
5.1.2  Stack Temperature Sensors - The  stack temperature sensors
(thermocouples and thermometers) should be compared with a refer-
ence thermometer  or with  a thermocouple  if the  temperature is
>405°C (761°F).
     For thermocouple(s),  compare  the thermocouple  and  the  ref-
erence  thermometer  readings  at   ambient  temperature.   If  the
values agree within  ±1.5%  of the  absolute temperature, the cali-
bration  is  valid;  if not,  recalibrate  the thermocouple  (Section
3.9.2) to  determine  the difference (AT )  in the absolute average
                                       s
stack temperature  200°C  (360°F) if T  is between 200°C and 405°C.(360° and
                          5
751°F).   Compare  the stack thermometer with a  thermocouple  at a
temperature  that  is within  ±10%  of T  if T^ is >405°C (761°F).
                                      S      S
If  the  absolute temperatures  agree within ±1.5% the calibration
is  valid;  if not,  determine the error AT^ to correct the average
stack temperature.
5.1.3  Barometer  -  The  field barometer should be compared to the
mercury-in-glass  barometer.   If the readings agree within ±5 mm
(0.2 in.)  Hg,  the field readings are acceptable; if not, use the
lower value  for  the calculations.   If  the field  readings are
lower than the  mercury-in-glass  readings,  the field  data are
acceptable;  if not, use the difference in the  two readings  (the
adjusted barometric  value)  in  the calculations.
5.2 Base  Laboratory Analysis
     All fluoride samples  should be checked by the analyst upon
receipt  in  the base  laboratory  for  identification  and sample
o

-------
                                              Section No.  3.9.5
                                              Revision No.  0
                                              Date January 4,  1982
                                              Page 5 of 19

 integrity.  Any losses should be noted on the analytical  data form
 (Figure 5.2).  Either void the sample or correct the data using a
 technique approved by the  administrator.   If a noticeable amount
 of sample has  been lost by leakage, the  following procedure may
 be used to correct the volume.
      1.    Mark  the new  liquid  level  on  the sample  container.
      2.    Treat the ' sample as described  in  Subsection 5.2.3 and
 note  the final dilution volume (V  ,  ).
 ,-jf-                               so In
      3.    Add  water  up  to the  initial  mark  on  the  container,
 transfer the water to a graduated cylinder and record the initial
 sample volume (vsoini) in milliliters.
      4.    Add water  to  the new mark on  the  container. -Transfer
 the water to a graduated  cylinder,  and record  the  final volume
 (V ,  -) in  millileters.
      5.    Correct  the  volume  by using  the  following equation:

                V      = V      Vsolni
                 soln1     soln  V  ,  f
                                 solnf
 where
      V  ,  ,  = sample volume to  be used in the  calculations,  ml;
       V  .   = total volume of solution  in which  fluoride is  con-
        soln
               tained,  ml;
      V  ,  .  = initial volume added to the container in the field,
               ml;
      Vsolnf = f^nal  v°lume  removed from the container in the base
               laboratory, ml.
      6 .    Both the  corrected  and uncorrected  values should  be
'Submitted in the  test report to the agency.
      This analytical method is  based on measurement of the activ-
 ity  or  concentrations of fluoride  ions  (F~)  in aqueous samples  by
 use   of  an  appropriate  calibration  curve.   Fluoride  activity
 depends,  however,  upon the  total ionic  strength of the sample and
 the  electrode does  not respond to  fluorides  which  are  bound  or
 complexed.    This  difficulty  is  largely  overcome  by  adding  a
 buffer  of high total  ionic  strength  and by requiring preliminary
 distillation to  eliminate interferent  ions.   The  sample  response

-------
                        -1-er //
    Date
                    U  er
                                 yes
Sample location

Samples identifiable

Ambient temperature     £ Q. 5"° (L__

Temperature of calibration standards

Temperature of samples    £.&. 5"° 0—
                                       Li
    Analyst
no  All liquid levels at marks
                                                       Constant temperature bath used 	

                                                       Date  calibration standards prepared
Sample
number
/9F-/
ftp-a
f)F-3
fiF-4





Sample
identification
number
AF - no
rtF-iAO
AF-J30
#F- 140





Total
volume of
sample,
(Vt), ml
/ooo
/OOO
1 f)f>£>
I ODO





Aliquot
total sam-
ple added
to still
(At), ml
/&&
J OO
/ 06
J 06





Diluted
volume of
distillate
collected
(Vd), ml
^?5^>
3.5'C>
3
380
£37





Concentration
of fluoride
from cali-
bration curve,
(M), molarity
f>. Oooo 7*t
& .660 1 2.
Q.OOG&'J'b
O. 0OOQ 19-





Total
weight of
fluoride
in sample
(Ft), mg
3.S-/S~
s~.<*qq
j. /.Per
^.^70





Total weight of fluoride in sample
Ft =
Signature of analyst


Signature of reviewer or supervisor
                                                           Remarks:
                                 Figure 5.2   Fluoride  analytical  data sheet.
        O
        O
                                                             id rt < O
                                                              CD fT> H- ft
                                                                  W H-
                                                              CS\ C_i H- O
                                                                PJ O 3
                                                              O 0 2
                                                              H,I±   &:
                                                                p 2; o
                                                              M H O •
                                                              vi>^ •
                                                                    CO
                                                                                                                      Ul
                                                                03
                                                                M
                                                                                                              O

-------
                                             Section No.. 3.9.5
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 7 of 19

to  the ion-specific  electrode  is  also  monitored by  a standard
reference  electrode  and a modern  pH meter that  has an expanded
millivolt scale.
     Procedures  are  -detailed  herein  for  preparing  reagents,
blanks,  control samples,  distillation  aliguots,  reference  and
working standards  (including serial dilutions),  and an expanded
calibration  curve  and  procedure  for  treating,  separating,  and
measuring the fluoride in samples.
5.2.1   Reagents - The  following  reagents are needed for  the
analyses of fluoride samples.
     1.   Calcium oxide (CaO) -  ACS reagent grade  powder or ACS
certified grade containing £0.005% fluoride.
     2.   Phenolphthalein indicator -  0.1% in  1:1  ethanol-water
mixture (v/v).
     3.   Sodium hydroxide (NaOH) - Pellets, ACS reagent grade or
the equivalent.
     4.   Sulfuric acid (HgSO4) - Concentrated, ACS reagent grade
or the equivalent.
     5.   Filters - Whatman No. 541 or the equivalent.
     6.   Water - Deionized distilled to conform to ASTM specifi-
cation D1193-74, Type 3.   The analyst may omit the Mn04 test for
oxidizable  organic  matter  if  high  concentrations  of  organic
matter are not expected.
     7.   Total ionic strength adjustment buffer (TISAB)   -   Add
approximately 500 ml of distilled  water  to a l-£ beaker; to this
add  57 ml of  concentrated glacial  acetic  acid,  58 g  of sodium
chloride  and  4  g  of  CDTA  (cyclohexylenedinitrilotetraacetic
acid); and  stir to dissolve.   Place the beaker  in  a water bath
until it has cooled,  and then slowly add about 150 ml of 5M NaOH,
while  measuring  the  pH continuously with a calibrated pH elec-
trode  and a reference electrode pair,  until the pH is 5.3.  Cool
to room temperature, pour  into  a l-£ volumetric flask and dilute
to the l-£ mark with distilled water.
     8.   Hydrochloric acid  (HC1)   -   Concentrated   ACS  reagent
grade or the equivalent.

-------
O
                                             Section No. 3.9.5
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 8 of 19

     9.   Sodium fluoride (NaF) standard (0.1 M) - Dissolve 4.2 g
± 0.002 g ACS reagent grade NaF, which has been dried for a mini-
mum of 2 h at 110°C (230°F) and stored in a desiccator, in deion-
ized distilled water,  and dilute to 1-2 with deionized distilled
water; this solution contains 0.1 M of Fluoride.
5.2.2  Blanks  -  The three  blanks needed  for  the  analysis are a
filter blank to  ensure that the quality of the filter is accept-
able,  a  distillation blank to  avoid cross contamination,  and a
sample blank to  analyze with the samples to verify the purity of
the reagents used in sampling and analyses.
-.,
     1.   Filter blanks  - Determine the  fluoride  content of the
sampling  filters  upon  receipt of each new  lot and at least once
for  each  test series.    Randomly select three  filters  from each

                                                                    o
          1.   Add  each  filter to  500  ml of  distilled water.   ^-s
          2.   Treat the filters exactly  like a sample  (Subsec-
tion 5.2.3).
          3.   Use a 200  ml aliquot for distillation.  Initially,
the  filter blank must be <0.015 mg  F/cm2; if  not,  reject this
batch  and obtain a new  supply of filters.
     2.   Distillation  blank -  Check the condition of the acid in
the distillation flask  (Subsection 5.2.5) for  cross-contamination
after  every 10th sample  by adding 220 ml  of distilled water to
the  still  pot  and then proceed with the  analysis.  If detectable
amounts of  fluoride  (>0.00001 M) are found in the blank, replace
the acid in the distillation flask.
     3.   Sample blank  - Prepare the  sample  blanks in the field
at  the  same  time  and  with  the same  reagents used  for sample
recovery.
          1.   Add  an  unused  filter  from the same batch used in
sampling  to a  volume   of distilled water  equal  to  the average
amount used to recover  the  samples.

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                                             Section No. 3.9.5
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 9 of 19

          2.   Treat  the  sample blank in  the  same  manner as the
samples  are  treated  (Subsection  5.2.3).  Analyze  the  sample
blanks with the samples.
5.2.3  Sample Preparation  - Use  the  following procedure to pre-
pare  samples  for distillation.   Distillation  is  not required if
it  can be  shown to  the  satisfaction of  the  Administrator that
fluoride results  are  unaffected by the alternate analytical pro-
cedure (e.g.,  ash and  fusion  of particulate  matter  with subse-
quent ion selective electrode analysis, or direct electrode anal-
ysis of gases trapped in impingers).. - .
     1.   Filter the  contents  of the  sample container (including
the sample filter) through a Whatman No.  541 filter or the equiv-
alent  into  a  1500-ml  beaker; if the filtrate  volume  is  >_900 ml,
add NaOH to make the  filtrate basic to phenolphthalein,  and then
evaporate to <900 ml.
     2.   Place the Whatman No. 541 filter containing the insolu-
bles  (including  the  sample  filter) in a  nickle  crucible,  add a
few milliliters  of water;   and  macerate  the filter  with a glass
rod.
     3.   Add 100 mg  or sufficient quantity of CaO to the nickel
crucible to make the slurry basic; mix thoroughly; and add a cou-
ple drops of phenolphthalein indicator, which turns pink in a ba-
sic medium.   Note:   If the  slurry does  not remain basic (pink)
during/the  evaporation of  the  water,  fluoride will  be  lost;  if
the slurry becomes colorless,  it is acidic so  add  CaO  until the
pink returns.
     4.   Place the crucible either in a hood area under infrared
lamps  or on  a  hot  plate  at  low  heat  (approximately  50-60°C)
(122-140°F),  and  evaporate  the water  completely;  then  place the
crucible on  a hot  plate under a hood  and slowly  increase the
temperature for  several hours  or until  the  filter  is  charred.
     5.   Place the crucible in a cold muffle furnace and gradu-
ally  (to prevent smoking)  increase  the  temperature   to  600°C
(1112°F); maintain  the temperature  until the  crucible  contents
are reduced to an  ash containing no organic material; and remove
the crucible from the furnace to cool.                /'"""~~

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                                             Section No. 3.9.5
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 10 of 19          ^.^

     6.   Add  approximately  4 g  of  crushed NaOH pellets  to the
crucible, and  mix;  return the crucible to  the  furnace,  and fuse
the  sample  for  10  min  at 600°C  (1112°F);  and then  remove the
sample  from the  furnace, and cool  it to  ambient temperature.
     7.   Use  several rinsings  of warm distilled water to trans-
fer  the contents of the  crucible  to the beaker  containing the
filtrate (step  1) and  finally,  rinse the crucible with two 20-ml
portions of 25% (v/v)  H2S04,  and carefully add the rinses to the
beaker.
     8.   Mix  well,  and  transfer the  beaker  contents to  a 1-8,
volumetric  flask.   Record this  volume as  Vt  on  the  data form
(Figure  5.2).   Dilute  to volume  with distilled water,  and mix
thoroughly;  and allow any undissolved solids to settle.
     9.   Weigh the spent silica gel and report the weight to the
nearest 0.5  g on the sample integrity and recovery form.
5.2.4   Acid-water Ratio  - The acid-water ratio in the distilla-
o
tion flask should be adjusted by following this procedure.  Use a
protective shield when carrying out the procedure.
     1.   Place 400 ml of distilled water in the 1-2 distillation
flask,  and  add  200  ml  of  concentrated  H2S04.   Slowly  add the
H2S04, while constantly swirling the flask.
     2.   Add soft glass beads and several small pieces of broken
glass tubing, and  assemble  the apparatus as shown in Figure 1.3.
     3.   Heat the flask  until it reaches a temperature of 175°C
(347°F),  and discard  the  distillate,   and  hold  the  flask for
fluoride separation by distillation.
5.2.5   Fluoride Separation  (Distillation)   -   Fluoride  in  the
acid-water  adjusted  flask  can be  separated from  other  consti-
tuents in the aqueous sample by distilling fluosilicic  (or hydro-
fluoric) acid  from a solution of the sample  in an  acid  with a
higher boiling  point.   Samples with  low concentrations"of fluo-
ride  (e.g.,  samples  from  an  inlet  and  outlet of  a^ scrubber)    ^_^^
should be distilled first to eliminate contamination by carryover    f  J
of  fluoride  from the previous sample.   If fluoride distillation
in  the  milligram range  is to  be  followed by distillation in the
fractional  milligram  range,  add  200 ml of  deionized distilled     /<_/

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                                             Section No. 3.9.5
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 11 of 19

water  and redistill  similar to  the acid  adjustment procedure,
Subsection 5.2.4,  to  remove residual fluoride from the distilla-
tion system.
     1.   Cool the contents of the distillation flask (acid-water
adjusted) to <80°C (176°F).
     2.   Pipette an aliquot of sample containing <10.0 mg F into
the  distilling flask,  and add distilled  water to make  220 ml.
The  aliquot  size  (A, )  should be entered on the data form (Figure
5.2).  Note;   For an estimate of  the  aliquot size that contains
<_10 mg F, see Subsection 5.2.6.
     3.   Place a  250-ml  volumetric  flask at the condenser exit;
heat the distillation flask as rapidly as possible with a burner,
while  moving the  flame up  and  down the  sides of the  flask to
prevent bumping; conduct  the distillation as rapidly as possible
(<_15 min).   Slow  distillations  have  been found to give low fluo-
ride  recovery.   Collect  all  distillate  up  to  175°C  (347°F).
Caution;    Heating >175°C   (347°F) will cause  H-SO^  to  distill
over.  Note;   The H2SC-  in the  distilling flask can  be reused
until carryover of interferent or until poor fluoride recovery is
shown in the distillation blanks and the control samples,
     4.   Before distilling  samples  and after every 10th sample,
distill a  control  sample to check the  analytical procedures and
interferences (Subsection 5.2.6).
5.2.6  Control Sample - A control sample should be used to verify
the  calibration  curve  and  the  analytical procedures  before and
during the  analysis  of  the field  samples.   Use the  following
procedures.
     1.   The 0.05M NaF control sample stock solution -  Add 2.10
g of reagent grade anhydrous NaF  to a  l-.fi.  volumetric flask; add
enough distilled water to dissolve;  and dilute  to l-£  with dis-
tilled water.
     2..   The 0.005M NaF working solution - Pipette 100 ml of the
0.05M NaF  stock solution  into  a l-£ volumetric flask, and dilute
to the mark  with  distilled water to get the  0.005 M NaF working
solution.   Note;  The  control  should be within 0.004M and 0.006M
NaF; if not,  take corrective action until  these  limits are met.

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                                             Section No.  3.9.5
                                             Revision No.  0
                                             Date January 4,  1982
                                             Page 12 of 19

     3.   Analyze the working  solution  in the same manner as the
samples  are  analyzed  (Subsections  5.2.5,  5.2.9,  and  5.2.10).
5.2.7  Distillation Aliquot -  The  sample volume for distillation
should contain <10 mg F.  Use the following procedure to estimate
the aliquot size.
     1.   Pipette a  25»ml aliquot of sample  into a polyethylene
beaker.
     2.   Add  an equal  volume  of TISAB  buffer,  and mix well.
     3.   Adjust the  pH meter,  and  read the millivolts'  for the
nondistilled sample and  the  calibration standard solutions (Sub-
section 5.2.8).
     4.   Determine the  molarity of  the nondistilled sample from
the calibration  curve,  and determine the size of the aliquot for
distillation by substituting the molarity (M) of the nondistilled
sample in the following equation:                                    (J
     .liquot for distillation  (1, = e^LSdVmolarity  (M)
The aliquot size is  only an approximation since the interferring
ions have  not been removed by distillation.   If the estimate is
>220 ml,  use  220 ml;  if it is  <220 ml,  add distilled water to
make the  total  volume 220 ml;  if  required,  dilute the sample to
get a minimum 1-ml aliquot.
5.2.8  Calibration Standards - Use  the 0.1M NaF reference stan-
dard (Subsection 5.2.1)  'in the following procedure for preparing
serial dilutions.
     1.   Pipette  10  ml of 0.1M  NaF  into  a  100-ml  volumetric
flask,  and  dilute  to  volume with  distilled water  to  get a 0.01M
standard.
     2.   Pipette 10  ml  of the 0.01M standard solution to make a
0.001M solution in the same manner, and so on to make 0.0001M and
0.00001M solutions.
     3.   Pipette 50  ml of each of the  standard  solutions  into    (  J
separate polyethylene beakers,  add 50 ml of TISAB buffer to each,
and mix well (50 ml of 0.01M diluted with 50 ml of TISAB is still
referred to as  0.01M).   Prepare  fresh  0.01M NaF standards daily.

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                                             Section No. 3.9.5
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 13 of 19

A  detailed explanation  is  in  Section  3.9.2, Subsection  2.8 of
this method along with calibration curves (Figures 2.8 and 2.9 of
Section 3.9.2).
5.2.9  Sample Treatment  - To  treat the  distilled fluoride in the
volumetric  flask (from  Subsection 5.2.5,  step  3),  follow  this
procedure.
     1.   Dilute with  distilled water to the  250-ml  mark on the
volumetric flask at the condenser exit,  and mix thoroughly.
     2.   Pipette 25-ml  of the sample  into  a  50-ral volumetric
flask, dilute  to the  mark with  TISAB  buffer solution,  and mix
well.
     3.   Bring the calibration standards  and the samples to the
same  temperature; if  the ambient  laboratory  temperature fluctu-
ates more than ±2°C (4°F), condition the samples and standards in
a constant temperature bath.
5.2.10   Concentration  Measurement  -  Some electrodes  yield posi-
tive  (direct  F~ concentrations)  and some  yield negative (indi-
rect) values;  if positive,  recalibrate  the electrode by using a
manufacturer-recommended  standard,  by adjusting the  calibration
control  (if needed)  to  the correct  value,  and  by verifying the
calibration after measuring each  standard  and sample to prepare
the calibration curve.
     Several precautions  are  needed before beginning the .proce-
dure.
     1.   Keep the pH  meter on standby,  and rinse between  mea-
surements .
     2.   Keep the electrodes  in  the storage  solution to prevent
overdrying  if  long periods  of time are expected  between uses.
     3.   Do not allow  the  electrode to  touch  the  side  of the
beaker during or between measurements.
     4.   Use of a stirrer will minimize electrode response time,
but stirring a solution before immersing the electrode may entrap
air around the crystal and  cause  needle fluctuations and errone-
ous readings.

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       :'                                     Section No. 3.9.5
                                             Revision No.. 0
                                             Date January 4, 1982
                                             Page 14 of 19

     Use an ion-specific electrode in the following procedure for
measuring the F~ concentration.
     1.   Transfer  each  standard and each  sample  to  a series of
150-ml polyethylene beakers,  and arrange each series so that the
lowest  concentration will  be  read  first  to  avoid  carryovers.
     2.   Rotate the switch of the pH meter to standby, and allow
a 30-min warm-up period.
     3.   Raise  the electrode  from  the storage solution  in the
beaker, and rinse  either the electrode thoroughly with distilled
water  or soak  the  fluoride-sensing electrodes in distilled water
for  30 s before removing  and blotting  dry.   Note:    This step
should be done between each measurement.
     4.   Turn  the  adjustment  knob  to  calibrate;   immerse  the
electrode in the NaF standard of lowest concentration.
     5.   Rotate  the switch to  millivolts  (mV),  and  turn the      ^^
adjustment knob  to calibrate,  read  the millivolts of the known      \	J
buffer solution  from the meter,  and record  the  value on Figure
5.2.  Rotate the selector knob .to standby.
     6.   Raise  the electrodes  carefully  from the  buffer solu-
tion,  and rinse thoroughly  (step 3).
     7.   Immerse  the  electrodes  carefully  into a beaker  of
standard  solution,  and  set  the beaker  on a  magnetic stirrer.
Note;   If  stirrer generates  enough  heat to change solution tem-
perature,  place  insulating  material  (e.g.,  cork)   between the
stirrer and the beaker.
     8.   Rotate the  selector knob  to  mV,  read the  mV from the
meter, .and  record the value  on  Figure  5.2; allow the electrodes
to  remain in  the solution at least 3 min,  and rotate  the knob to
standby; take  a  final reading.
     9.   Repeat  the  above  steps  until  all samples  have been
read.  Switch  to standby, and then rinse and  store the electrodes
in  distilled water.
5.2.11  Expanded Calibration Curve  - Use the following procedure
to  construct  an  expanded calibration curve for analyzing samples
in  the lower concentration  range of <2 mg F/250 ml distillate and

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                                             Section No. 3.9.5
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 15 of 19

for more  accurate  determinations  of concentrations since samples
in  the  range  are  <0.001M  NaF.   Use  this  procedure  to prepare
calibration  standards,  using  the 0.1M NaF  standard  for serial
dilutions (Subsection 5.2.1).
     1.    Pipette  10  ml  of the  0.1M  NaF into  a  l-£  volumetric
flask, and dilute to volume using distilled water to get a 0.001M
standard.
     2.    Pipette  10  ml  of the  0.001M  standard,  and dilute it
to 100 ml to make a 0.0001M standard.
     3.    Pipette  10  ml of the  0.0001M  standard,  and dilute to
100 ml to make a 0.00001M standard solution.
     4.    Pipette  50  ml  of the  0.001M  standard  into  a 100-ml
volumetric flask,  and dilute  to  volume  with distilled  water to
get a 0.0005M standard.
     5.    Pipette  10  ml  of the  0.0005M  standard into  a 100-ml
volumetric flask,  and dilute to volume to make  a  0.00005M stan-
dard.
     6.    Calibrate the electrode,  and  construct a  calibration
curve (Subsection  5.2.8).  Note;   As shown in Figure  5.3,  the
nominal   concentrations  of 0.00001M, 0.00005M,  0.0001M,  0.0005M,
and 0.001M NaF should  be  plotted on the log axis and the elec-
trode potentials (mV)  are plotted on a linear scale.
     Control samples  are needed  to  verify the  expanded calibra-
tion  curve  and  the  analytical procedure before  and  during the
analysis  of  the field  samples.   Use  the 0.005M  control sample
(Subsection 5.2.1)  for the serial dilutions.
     1.    Pipette 5 ml of the 0.005M control sample into a 100-ml
volumetric flask, and dilute to volume to get a 0.00025M control.
     2.    Pipette  50  ml  of the  0.00025M control into  a poly-
ethylene beaker, add  50 ml of TISAB buffer,  mix well,  and use to
validate  the  calibration curve and  to provide  hourly checks on
the daily calibration.
     3.    Analyze  the  control  sample (Subsection  5.2.5),  and
record the data on the laboratory worksheet (Figure 5.4).

-------
i -

LU
I—
o
Q.

UJ
Q
O
o:
h-
o
LU
     140
     160
     180
     200
240
     260
     280
     300
                       -/<"i V
                            -f*
         Date     ~if^_L L

         Sample  temp

         Analyst 	

         Reviewer
cQ.s-rc
        0.00001
                                                                Molaritv

                                                                 0.00001
                                                                 0.00005
                                                                 0.0001
                                                                 0.0005
                                                                 0.001
                                                                 Control
                                                                  sample
                               0.00005        0.0001

                                      FLUORIDE  HOLARITY, M



                       Figure 5.3. .Expanded  fluoride calibration curve.
                                                                                      3 CO
                                                                                      al
                                                      0.0005
0.001
                                                                                                            *TJ O JO trt
                                                                                                            w p» n> n>
                                                                                                            iQ fl"  ^ •-•• o'
                                                                                                             'H
                                                                                                                  U)
                                                                                                                  cn
                                                                                                              CO
                                                                                                              NJ
    o
                                                   o
                                                                              o

-------
                                                    Section No.  3.9.5
                                                    Revision No.  0
                                                    Date  January 4,  1982
                                                    Page  17 of 19
Date standards prepared
                           LABORATORY  WORKSHEET

                                           Date
                                 /.
                                 V
                                                               /.
Temperature of standards     £0 .S~0 (2.       Electrode number _____ OO I
Standard number
1
2
3
4
5
Control sample
Concentration, M
0.001
0.0005
0.0001
0.00005
0.00001
o.aooA^
Electrode potential, mV
£07
£30
3oo
ay-*-
Note:   The  control sample, from the calibration curve, must be between
0.0002M and 0.0003M.
Signature  of  analyst

Signature  of  reviewer
             Figure 5.4.  Expanded calibration curve data form.

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                                                     Section  No.  3.9.5
                                                     Revision No.  0
                                                     Date January 4, 1982
                                                     Page 18  of 19
                                                                    o
            Table 5.1  ACTIVITY MATRIX  FOR  POSTSAMPLING OPERATIONS
Apparatus
•Sampling
Apparatus

Dry gas meter
Meter thermome-
  ters
Barometer
Stack tempera-
  ture sensors
Base Laboratory
Analysis

Reagents
Acceptance limits
±5% of calibration
factor
±6°C (10.8°F) ambient
temperature
±5 mm (0.2 in.) at
ambient pressure
±1.5% of the reference
thermometer or thermo-
couple
Prepare according to
Subsec 5.2
Frequency and method
   of measurements
Make three runs at a
single intermediate
orifice setting at
highest volume of
test (Sec 3.9.2)
Compare with ASTM
mercury-in-glass
thermometer after
each test
Compare with mercury-
in-glass barometer
after each test
Compare with ref-
erence temperature
after each run
Prepare a calibration
curve when preparing
new reagent
Action if
requirements
are not met
Recalibrate;
use factor
that gives
lower gas
volume
Recalibrate;
':se higher
temperature
for calcula-
tions
Recalibrate;
use lower
barometric
value for
calculations
Recalibrate;
calculate
with and
without tem-
perature cor-
rections
Prepare new
solutions and
calibration
curves
 (continued)
                                                                                     O
                                                                                     o

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                                                    Section  No. 3.9.5
                                                    Revision No. 0
                                                    Date January 4,  1982
                                                    Page 19  of 19
Table 5.1 (continued)
Apparatus
Acceptance limits
Frequency and  method
   of measurements
Action if
requirements
are not met
Control  sample
±2% when run with
fluoride standards and
±10% when distilled
and run with field
samples
Prepare new controls
before and during
analysis of field
samples
Prepare new
solution and
calibration
curve,  and/or
change  dis-
tillate
solution

-------
o
o
o

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                                             Section No. 3.9.6
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 1 of 7
6.0  CALCULATIONS
     Calculation  errors  due  to  procedural or  mathematical  mis-
takes can be  a large part of total system error.  Thus, each set
of calculations  should be  repeated or spotchecked, preferably by
a  team  member  other than  the  one that  performed the original
calculations.   If a difference  greater than a  typical roundoff
error is  detected,  the  calculations  should be  checked step-by-
step until the source of error is found and corrected.
     A computer  program  is advantageous  in reducing  calculation
errors.   If a standardized computer program is used, the original
data entry  should be checked and  if  differences  are  observed,  a
new computer run should be made.
     Table 6.1 at  the end  of  this section summarizes  the quality
assurance  activities  for  calculations.    Retain  at   least  one
significant  digit beyond  that  of  the  acquired  data.   Roundoff
after the final  calculations  for each run  or sample  to two  sig-
nificant  digits,  in accordance  with  ASTM 380-76.  Record  the
results  on Figure 6.1A or 6.IB.
6.1  Nomenclature
     Terms used in Equations 6-1  through 6-7 are defined here for
use in the Subsections that follow.
      n
     B
      ws
      tb
                                    2    2
= Area of nozzle, cross-sectional, m  (ft )
= Aliquot of total sample added to still, ml
= Water vapor in the gas stream, proportion by
  volume
= Concentration of fluoride in stack gas corrected
  to standard conditions of 20°C, 760 mm Hg (68°F,
  29.92 in. Hg) on dry basis, mg/m  (Ib/ft )
= Total weight of fluoride in sample, mg (Ib)
= Total weight of fluoride in sample blank,  mg (Ib)
= Percent of isokinetic sampling, %

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                                              Section No. 3.9.6
                                              Revision No. 0
                                              Date January 4, 1982      (j
                                              Page 2 of 7
                   SAMPLE VOLUME (ENGLISH UNITS)

vm = £ 8.  • &4 7 ft*,  T  = S 3 A -  £ °R, PX3>. = <3 9  • 
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                                              Section No. 3.9.6
                                              Revision No., 0
                                              Date January 4,  1982
                                              Page 3 of 7
                   SAMPLE VOLUME (METRIC UNITS)

V  = /  . 3 2 % ro3,  T™  = 3 / O . & °K, p. _ = 7 V A  . O mm Hg
 IB   ~~   ~~ ~^ ~~      in    — — —   —      D&JL   — — •—   —

Y = 0 . £ 9 <£, AH  = ,2  6 .  0 mm H2O

                       Pb  + (AH/13.6)               3
Vm(std) = °-3858 vm y       T	 = L - -2 ^ 2 m   Equation  6-1
                   FLUORIDE CONTENT IN SAMPLE

   = / O O O . <9ral, A.  =/ 0<9.  <2>ml, V. = <3 5" 0 . O
     ""•"       ~"       U   ~ — —•   —      Q   — —. _   _

    £ • e Q Q ££K

        vi- vri
   = 19  &. u M = A  . 3 7 5*mg                       Equation  6-4
                  -
            CONCENTRATION OF FLUORIDE (METRIC UNITS)

Vm(std) = - ' - ^ % dscm,  Ft = ^ .  J 7 5", F^ = tf> . £ 5 O mg

     F  ~ F
       -
       m(std)
      t ~  tb
C  = -^ - ~ = _/  . £ 7 2? mg/dscm                    Equation  6-5
 5
     All other equations  same as Methods 2 and 5.
    Figure 6.IB.  Fluoride  calculation form (metric units).

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                                        Section No. 3.9.6
                                        Revision No. 0
                                        Date January 4, 1982
                                        Page 4 of 7


M       = Concentration of fluoride from calibration curve,
          M

M       = Molecular weight of water, 18.0 g/g-mole
          (18.0 Ib/lb-mole)

P-      = Barometric pressure at sampling site, mm  (in.) Hg

P       = Absolute stack gas pressure at sampling site, mm
          (in.) Hg

Pstd    = standard absolute pressure, 760 mm (29.92 in.) Hg
                                              3
R       = Ideal gas constant, 0.066236 mm Hg-m /K-g-mole
          (21.83 in. Hg-ftV°R-lb-mole)

T       = Absolute average dry gas meter temperature,
          vi OD ^
          t\ \- t\)

T       = Absolute average stack gas temperature, K (°R)
 s

Tstd    = standard absolute temperature, 293K  (528°R)

V.,      = Volume of distillate collected, ml
 a,

V.      = Total volume of liquid collected in impingers and
          silica gel, ml.  (Volume of water in silica gel =
          grams of silica gel weight increase x 1 ml/g;
          volume of liquid collected in impinger =  final
          volume - initial volume)
 m
= Volume of gas sample measured by dry gas
  meter, dcm (dcf)
^m(std) = V0!111116 °f 9as sample measured by dry gas meter
  *   '   corrected to standard conditions, dscm (dscf)

V       = stack gas velocity calculated by Method 2 (Equa-
          tion 2-7) using data from Method 13, m/s (ft/s)

Vt      = Total volume of sample, ml

V ,   ,. = Volume of water vapor in gas sample corrected to
  *   '   standard conditions, scm (scf)

Y       = Dry gas meter calibration factor                               -^

AH      = Average pressure differential across the orifice              V	/
          meter, mm (in.) H2O

p.,      = Density of water, 1 g/ml (0.00220 Ib/ml)
 W                                                            ,.^f

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                                             Section No. 3.9.6
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 5 of 7

     6       = Total sampling time, min
     13.6    = Specific gravity of mercury
     60      = s/rain
     100     = Factor for converting to percent, %
6.2  Dry Gas Volume,, Corrected to Standard Conditions
     Correct  the  sample  volume  measured by  the  dry  gas  meter
(Vm) to standard conditions (20°C and 760 mm Hg or 68°F and 29.92
in.  Hg)  by using Equation 6-1.  The absolute  dry  gas meter tem-
perature  (Tm)  and orifi<
averaging the field data.
perature  (T )  and  orifice pressure  drop  (AH)  are obtained  by
            V       = V Y 	
             m(std)    m   T

                              Pb,r + (AH/13.6)
                    = Kl VmY       T	        Equation 6-1.
                                    m
where
     K., = 0.3858 K/mm Hg for metric units, and
        = 17.64 °R/in. Hg for English units.
Note:  If the  leak rate observed during any mandatory leak check
exceeds the acceptable  rate,  the tester shall either correct the
value of Vm in Equation 6-1  (Subsection 3.2.6,  Method 3),  or in-
validate the test runs.
6-3  Volume of Water Vapor
            Vw(std) = Vic              = K Vic         Equation 6-2

where
      K = 0.00133 m3/ml for metric units,  and
        = 0.04707 ft3/ml for English units.
                                                    (P-

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                                             Section No.  3.9.6
                                             Revision No.  0
                                             Date  January 4, 1982
                                             Page  6  of  7
6.4  Moisture Content of Stack Gas
                                                       Equation 6-3
                        m(std)    w(std)
Note;   If liquid  droplets  are in  the gas  stream,  assume  the
ctream  to be  saturated;  use  a  psychrometric  chart to  obtain
estimate of the moisture percentage.
6.5  Fluoride Content in Sample (Concentration)
= K
               vt
               ^ (V
                                                       Equation 6-4
where
     K = 19 mg/mmole for metric units,
     K = 4.19 x 10 5 Ibs for English units.
6.6  Concentration of Fluoride in Stack Gas
     C  =
                  . .
                                                     Equation 6-5
              m(std)
     K = 1.00 m3/m3 for metric units
     K = 35.31 ft3/m3 for English units.
     Isokinetic Variation (I)
     The isokinetic  variation (I) can  be  calculated  from either
raw  data  or intermediate values  using the  following equations.
6.7.1  Calculation of I from Raw Data
6.7
                                                                       s~*\
                                                                       f)
         100 x Tg [K Vic + (Y Vm/Tm)  (Pbar + AH/13.6)]

                                                     Equation 6-6
                       608vsPsAn
where
      K = 0.003454 mm Hg-m3ml-K for metric units, and
        = 0.002669 in. Hg-ft3/ml-°R for English units.
6.7.2  Calculations of I from Intermediate Values
              x Ts Vm(std) Pstd
         Tctd vc e
                        60
                                                     Equation 6-7
                                                                        o

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                                                  Section No.  3.9.6
                                                  Revision No.  0
                                                  Date January 4, 1982
                                                  Page 7 of  7
        = K
                 T  V
                 1s vm(std)
where

       K = 4.320 for metric units,  and

         = 0.09450 for  English  units.

6.7   Acceptable Results
      If  90%  <.  I  <. 110%,  the  results  are  acceptable.    If the

results are  low in comparison  to the standards  and if  I  is beyond
the  acceptable  range,  the administrator may  opt to  accept the
results; if  not,  reject the results and  repeat  the test.
Apparatus
Analysis data
  form
Calculations
Isokinetic
  variation
                 Table 6.1  ACTIVITY MATRIX FOR CALCULATIONS
Acceptance limits
All  data and calcula-
tions  given
Difference between
check and original
calculations within
roundoff error; one
decimal figure re-
tained beyond that of
acquired data
90% <  I < 110%; see
Eqs 6-6 and 6-7 for
calculation of I
Frequency and method
   of measurements
Visual  check
Repeat  all calcula-
tions starting with
raw data for hand
calculations; check
all raw data input
for computer cal-
culations and hand
calculate one sample
per test
Calculate I for
each traverse point
Action if
requirements
are mot met
Complete  the
missing data
values
Indicate
errors  on
analysis data
form
Repeat test;
adjust flow
rates to
maintain  I
within ±10%
variation

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                                             Section No. 3.9.7
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 1 of 3
7.0 MAINTENANCE
     Normal  use  of  emission  testing equipment  subjects  it  to
corrosive  gases,  temperature  extremes,  vibrations,  and  shocks.
Keeping  the  equipment in  good operating order over  an extended
time requires routine maintenance and knowledge of the equipment.
Maintenance  of the  entire  sampling train  should be  performed
either quarterly or after 1000 ft  of operation, whichever occurs
sooner.   Maintenance  activities  are summarized in Table 7.1  at
the end  of this section;  the following routine checks are recom-
mended, but not required,  to increase reliabilty.
7.1  Pump
     Several  types  of pumps  are  used  in  commercial  sampling
trains;  two of the  most common  are the fiber  vane  pump with
in-line  oiler  and  the diaphragm pump.  The fiber vane pump needs
a periodic check of the oil and the oiler jar.   Used oil (usually
nondetergent or machine weight) should be about  the  same trans-
lucent color as unused or spare oil.  When the pump starts to run
erratically  or when  the  head  is  removed each year,  the  fiber
vanes should be changed.
     The  diaphragm pump   requires  little maintenance.   If  the
diaphragm pump leaks or runs erratically, it is normally due to a
bad diaphragm  or to malfunctions in  the  valves;  these  parts arc
easily replaced, and  should  be cleaned annually by complete dis-
assembly of the train.
7.2  Dry Gas Meter
     The  dry  gas  meter  should be  checked for  excess  oil  and
component  corrosion by removing the  top plate every 3 mo.  The
meter  should be  disassembled,  and  all  components  cleaned  and
checked  more often if the dials show erratic  rotation  or if the
meter will not calibrate properly.

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                                             Section No.  3.9.7
                                             Revision No.  0
                                             Date January 4,  1982
                                             Page 2 of 3
o
7.3  Inclined Manometer
     The fluid  should be changed when it is  discolored,  or when
it contains  visible matter, and when  it  is  disassembled yearly.
No  other  routine  maintenance  is  required  since  the  inclined
manometer  is checked  during  the leak checks of both  the  pitot
tube and the entire meter box.
7.4  Sampling Train
     All other sample train components should be visually checked
every  3 mo,  and  they  should  be  completely  disassembled  and
cleaned  or replaced  yearly.   Many of the  parts/  such  as  quick
disconnects,  should be replaced when damaged rather than  after
they  are periodically checked.   Normally,  the  best  maintenance
procedure  is to  replace  the entire  unit—for example,  a  meter
box,  sample box, or umbilical cord.
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                                                      Section No.  3.9.7
                                                      Revision No.  0
                                                      Date January 4, 1982
                                                      Page 3  of 3
          Table 7.1  ACTIVITY MATRIX FOR  EQUIPMENT MAINTENANCE CHECKS
Apparatus
Fiber vane pump
Diaphragm pump
Dry gas meter
Inclined manom-
  eter
Other sampling
  train com-
  ponents
Nozzle
Acceptance limits
Leak free; required
flow; no -erratic be-
havior
Leak-free valves func-
tioning properly; re-
quired flow
No excess oil,  corro-
sion, or erratic dial
rotation
No discoloration of or
visible matter in the
fluid
No damage or leaks;  no
erratic behavior
No dents,  corrosion,
or other damage
Frequency and method
   of measurements
Periodic check of oil
and oiler jar; remove
head yearly and
change fiber vanes
Clean valves during
yearly disassembly
Check every 3 mo for
excess oil or corro-
sion; check valves
and diaphragm if
dial runs erratically
or if meter will not
calibrate
Check periodically;
change fluid during
yearly disassembly
Visually check every
3 mo; disassemble and
clean or replace
yearly
Visually check be-
fore and after each
test run
Action if
requirements
are not met
Replace as
needed
Replace when
leaking or
when running
erratically
Replace parts
as needed, or
replace meter
Replace parts
as needed
If failure
noted, re-
place meter
box, sample
box, or um-
bilical cord
Replace noz-
zle or clean,
sharpen, and
recalibrate

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                                             Section No. 3.9.8
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 1 of 7
8.0  AUDITING PROCEDURES
     An audit is an independent assessment of the quality of data
collected during  all  source tests,  especially those required for
enforcement.  "Independent" means that the individual(s) perform-
ing  the  audit and the standards and  equipment  used in the audit
are  different from the regular field team  and  the standards and
equipment used  in the source  test.  A  source  test for enforce-
ment comprises  a  series  of runs at one source.   Although quality
assurance  checks   by  a  field  team  are necessary  for routinely
generating  good quality data,  they are  not  part of the auditing
procedure.   Table  8.1  at the end of  this  section summarizes the
quality assurance  activities for the  auditors.
     Based  on a  collaborative  test1 of Method 13B,  performance
audits are recommended for—
     1.   The sampling  train volumetric flow  measuring  device,
     2.   The analytical phase,  and
     3.   The data processing.
In  addition  to  the  three performance  audits,  a system  audit
should be conducted as specified by the quality assurance coordi-
nator.   The performance  and  the system audits  are  detailed in
Subsections 8.1 and 8.2.
8.1  Performance Audits
     Performance  audits—independent  checks by  an  auditor  to
assess  data produced  by  the  total  measurement  system  (sample
collection  and  analysis,  and data  processing)—are quantitative
appraisals of data quality.
8.1.1  Audit of Sampling  Train Volumetric Flow  Metering Device  -
     The audit procedure described in this subsection can be used
to determine  the  accuracy  of the  flow metering  device (dry gas
meter) in a sampling train.  The dry gas meter is audited using a
calibrated  critical  flow  orifice housed in  a quick-connect cou-
pling and the following procedure:

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                       p    +  AH
v.td> • v i-if j  (bi;td 13-6)             E^ati°n s-1
             - v  V Y I  bar   13.6
                                             Section No.  3.9.8
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 2 of 7

     1.   Remove the critical orifice from its case and insert it
into the gas  inlet  quick-connect coupling on the source  sampling
meter box.
     2.   Turn the power to  the meter box on and start the pump;
     3.   Completely open the coarse  flow rate control valve and
close  the  fine  flow rate control valve to give  a  maximum vacuum
reading.  Caution:  A vacuum reading  of <425 mm (17 in.) Hg will
result in flow rate errors.
     4.   Allow  the orifice  and  source  sampling  meter box  to
warmup  for 45 min  with flow controls adjusted as  described in
step 3  before starting quality assurance runs.  If  the  audit is
made at the conclusion of  the  sample run,  the  warmup period is
not necessary.
     5.   Make triplicate quality  assurance  runs.   For each run/
record  the  initial  and the  final dry  gas meter  volumes,  the dry       /^.
gas  meter  inlet  and  outlet  temperatures,  the  internal  orifice       V_y
pressure drop  (AH),  the ambient temperature,  and  the barometric
pressure.   The  duration of  the  run should be  slightly  >15 min.
The  following procedure is  recommended and should  be performed
three  times to provide  the  required triplicate quality assurance
runs:   15  min after a  run  is  started, watch the dry gas  meter
needle  closely.   As  the needle reaches the  zero  (12  o'clock)
position, stop the pump and stopwatch simultaneously.  Record the
dry gas meter volume and the time.
     6.   Calculate  the corrected  dry gas  volume for  each run
using Equation 8-1.  For each replicate, record the corrected dry
gas  volume in  dry standard  cubic meters,  the  sampling time in
decimal  minutes,  the barometric  pressure in millimeters  of Hg;
and the ambient temperature in degrees celcius.
                                                                       o

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                                             Section No. 3.9.8
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 3 of 7

     Responsible, control  agencies  can obtain a calibrated criti-
cal  orifice (when  available)  prior  to  each  enforcement  source
test, conduct  the  audit,  and return the orifice and data form to
EPA  for evaluation.   Orifices  may  be obtained from  the  Source
Test Audit coordinator, Quality Assurance Division, Environmental
Monitoring  Systems  Laboratory,  USEPA,  Research  Triangle  Park,
North  Carolina 27711.   It  is  also  suggested  that organizations
that conduct  compliance tests participate  in  the  .EPA semiannual
audit of volume meters.
8.1.2   Auditsof  the  Analytical Phase  -   The  two  recommended
performance audits should be performed once during every enforce-
ment source  test as two  steps:    (1)  an  optional  pretest audit,
and  (2) a  mandatory audit during  the  analysis  of  the  field sam-
ples.
8.1.2.1  Pretest Audit of Analytical  Phase  (Optional)  - The pre-
test audit  for determining  the  proficiency of  the  analyst,  the
accuracy of the analytical  procedure,  and the accuracy  of the
standards  should  be performed  at  the discretion of  the  agency
auditor, by using  aqueous sodium fluoride  (NaF) samples provided
to the  laboratory  before the  enforcement source  test.  The NaF
samples may be prepared by the same procedures used for preparing
control samples (Section 3.9.5).
     The pretest audit is especially recommended for a laboratory
with  little or  no  experience  with  the Method  13B  analytical
procedure  (Section  3.9.5).   The  laboratory  should notify  the
agency/organization requesting the performance test of the intent
to test 30  days before  the  enforcement source  test,  and  should
request that   the  following audit samples  be  provided:   a  l-£
sample  for a  low concentration   (0.2 to  1.0 mg  F/dscm of  gas
sampled or  approximately 1  to 5  mg NaF/S.  of  sample)   and  a  1-jfc
sample  for  a  high  concentration   (2.0 to 10.0  mg F/dscm of  gas
sampled or approximately  10  to  50  mg NaF/£ of sample).  At least
10 days before the  enforcement  source test, the agency/organiza-
tion  should provide  the  audit  samples.   The  laboratory  could
                                                                 /  V\
analyze the low  and high concentrations, and  submit the results',
to the  agency/organization  before the enforcement  source  test.

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                                             Section No.  3.9.8
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 4 of 7

Note:   The  analyst performing  this  optional audit  must perform
the field sample analysis also (Subsection 8.1.3).
     The agency/organization determines the percent accuracy, %A,
between the  measured and the  known  concentrations  of the audit
sample using Equation 8-2.

            C (M)-C (A)
     % A =   c r   '	  100                         Equation 8-2
                                                                      o
where
     .Cp(M) = concentration  of the  audit  sample measured  by lab
             analyst, mg/ml, and
     Cp(A) = known  concentration  of  the  audit  sample,  ing/ml.
The %A is  actually a measure of the inaccuracy of the analytical
phase.
     The control  limits  for %A is expected to  be  within ±12% of
true value.
6.1.2.2  Audit of the Analysis (Mandatory) -  The purpose of this
mandatory audit is  to  assess the data quality at the time of the
analysis; this audit is  useful in checking computer programs and
manual methods of data processing.  The agency should provide two
audit samples  to  be analyzed  along with the  field samples.  The
percent  accuracy   (%A)  of  the  audit  samples  (determined using
Equation 8-2)  should be included  in the  enforcement source test
report as  a measure of the  inaccuracy (bias  and  imprecision) of
the analytical phase of  Method 13B during the actual enforcement
source test.
8.1.3  Audit of Data Processing  - Data processing  errors  may be
determined  by independent   (audit)  calculations,   starting with
data on  the field  and  laboratory data forms.   If a difference,
other than  roundoff error  is  detected between the original and
the  audit  calculations,  check all data  calculations.   Alterna-
tively,   the data  processing  may be  audited  by   providing the
testing  laboratory  with  specific  data sets  (exactly  as would
occur in the  field)  and by  requesting that  the results  of the  /  /
data calculations be returned to the agency/organization.         • //
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                                             Section No. 3.9.8
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 5 of 7

8.2  System Audit
     A  system  audit—an on-site inspection and review of quality
assurance checks  on the total measurement system (sample collec-
tion and analysis,  data  processing,  etc.)—normally  is a quali-
tative  appraisal of data  quality.
     Initially,  a system audit  is•recommended for each enforce-
ment source  test.  After the  field team has  acquired sufficient
experience with the method, the  frequency of system audits may be
reduced—for  example,  to one of  every four  enforcement source
tests.
     The auditor,  i.e.,  the  person performing the system audit,
should have extensive experience in source sampling, specifically
with the measurement system being audited.  The auditor's respon-
sibilities are as follows:
     1.   Inform  the  field team of the results  of pretest per-
formance audits, and specify any needed attention or improvement.
     2.   Observe the procedures and techniques used by the field
team during sample collection.
     3.   Check/verify   the   records  of  apparatus  calibration
checks   and the  quality  control charts  used  in  the  laboratory
analysis of control samples from previous source tests, if appli-
cable.
     4.   Forward the  results of the  system audit  to  field team
management  so that appropriate  corrective action may  be  ini-
tiated.
While on-site,  the  auditor should  observe  the field  test team's
overall.performance, including the following:
     1.   Setting up and  leakchecking the sampling train.
     2.   Preparing the  absorbing  solution, and adding it to the
impingers.
     3.   Checking the isokinetic sampling.
     4.   Conducting the posttest leak check.
     5.   Conducting the  sample recovery,  and checking the data
integrity.
Figure  8.2  is a checklist suggested for use by the auditor.  /   /i |
                                                              I?

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                                             Section No.  3.9.8
                                             Revision No.  0
                                             Date January 4,  1982
                                             Page 6 of 7
                                                                 o
res
NO
Comment
         JO'
OPERATION
                              Presampling Preparation

                    1.    Knowledge of process conditions
                    2.    Calibration of equipment,  before each
                         field test
                         On-Site Measurements

               3.   Sample train assembly
               4.   Pretest leak check
               5.   Isokinetic sampling
               6.   Posttest leak check
               7.   Record process conditions during sample
                    collection
               8.   Sample recovery and data integrity
                              Postsampling

                    9.   Accuracy and precision of control sample
                         analysis
                   10.   Recovery of samples for distillation
                   11.   Calibration checks
                   12.   Calculation procedure/check
General Comments:
                                                                 O
                                                                      O
        Figure 8.1.  Method 13B checklist for auditors.

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                                                     Section No. 3.9.8
                                                     Revision No.  0
                                                     Date January  4,  1982
                                                     Page 7  of 7
              TABLE 8.1.   ACTIVITY MATRIX  FOR AUDITING PROCEDURES
Audit
Performance
Audit

Analytical
  phase of
  Method 13B
  using aqueous
  sodium fluo-
  ride
Data processing
  errors
System audit
Acceptance 1i mi ts
Measured concentrations
of audit sample within
±12% of true value
Difference between
original and audit
calculations within
roundoff error
Operation technique as
described in Section
3.9
Frequency and method
   of measurement
Once during every
enforcement source
test; measure audit
samples and compare
their values with
known concentrations
Once during every
enforcement source
test, perform inde-
pendent calculations
starting with data
recorded on field
and laboratory forms
Once during every
enforcement test,
until experience
gained and then
every fourth test,
observe techniques;
use audit checklist
(Fig 8.2)
Action if
requirements
are not met
Review
operating
technique
Check and
correct all
data; recal-
culate if
necessary
Explain to
team devia-
tions from
recommended
techniques;
note on
Fig 8.2

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                                             Section No.  3.9.9
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 1 of 1
9.0  RECOMMENDED STANDARDS FOR ESTABLISHING TRACEABILITY
     To  acquire data  of  good quality,  two  considerations  are
essential:
     1.   The measurement  process  must be in  a  state  of statis-
tical control at the time of the measurement, and
     2.   The systematic  errors,  when  combined with  the  random
variations  (errors  of  measurement),  must  result in  acceptable
uncertainty.
Other quality assurance activities include quality control checks
and  independent  audits  of the  total  measurement system (Section
3.9.8); documentation of data by using quality control  charts (as
appropriate); use of materials, instruments,  and procedures that
can  be  traced to appropriate standards of reference;  and  use of
control standards and working  standards  for  routine data collec-
tion  and  equipment calibration.   Working  standards  should  be
traceable to primary standards:
     1.   Dry gas meter calibrated  against  a wet test  meter that
has been verified by  liquid  displacement (Section 3.9.2) or by a
spirometer.
     2.   Field  samples  analyzed  by comparisons  with  standard
solutions (aqueous NaF) that have been validated with independent
control samples.

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10.0    REFERENCE  METHOD
        Method 13B. Determination of Total Fluoride
        Emissions From Stationary Sources; Specific
        Jon Electrode Method

        I. Applicability and Principle
          1.1  Applicability.   Thl* method applies to
        the determination of fluoride (F) emissions
        from stationery sources as specified in the
        regulations. It does not measure
        fluorocarbons. such as freons.
          1.2  Principle.  Gaseous and paniculate F
        an withdrawn itokinetically from the source
        and collected in water and on a filter. The
        total F is then determined by the specific ion
        electrode method.

        2. Range and Sensitivity
          The range of this method Is 0.02 to 2.000 pg
        F/rnL- however, measurements of less than 0.1
        pg F/ml require extra care. Sensitivity has
        not been determined.

        S. Interferences
           Crease on sample-exposed surfaces may
        cause low F results because of adsorption.
               Section  Ho.  3.9.10
               Revision  No.   0

               Date  January  4,   1982
               Page  1 of  2


 4. Precision and Accuracy
   4.1  Precision.  The following estimates
 are based on a collaborative test done at a
 primary aluminum smeller. In the test, six'
 laboratories each sampled the stack
 simultaneously using two sampling trains for
 a total of 12 samples per sampling run.
 Fluoride concentrations encountered during
 the test ranged from 0.1 to 1.4 mg F/ra*. The
 within-laboratory and between-laboratory
 standard deviations, which include sampling
 and analysis errors, are 0.037 mg F/ra' with
 60 degrees of freedom and O058 mg F/m*
 with five degrees of freedom, respectively.
   4.2  Accuracy.  The collaborative test did
 not find any bias in the analytical method.

 S. Apparatus
   5.1  Sampling Train and Sample Recovery.
 Same as Method 13A. Sections  5.1 end ii
 respectively.
   5.2  Analysis.  The following items are
 needed:
   5.2.1  Distillation Apparatus, Bunsen
 Burner. Electric Muffle Furnace, Crucibles.
 Beakers,-Volumetric Flasks, Erlenmeyer
 Flasks or Plwtic Bottles. Constant
 Temperature Bath, and Balance.  Same as
 Method ISA, Sections SJ.1 to 5A9.
 respectively, except include also 100-ml
 polyethylene beakers.
   5.22  Fluoride Ion Activity Sensing
 Electrode.
   5.2.3  Reference Electrode.   Single
 junction, sleeve type.
  • 5.2.4  Electrometer.* A pH meter with
 millivolt-scale capable of iO.l-mv resolution.
 or a specific ion meter made specifically for -
 specific ion use.           	
   5.Z5  Magnetic Stirrer and TFE *
 Fluorocarbon-Coated Stirring Bars.

 6. R»agentt
   6.1  Sampling and Sample Recovery.
 Same as Method 13A. Sections  6.1 and 8i
 respectively.
   &2  Analysis.  Use ACS reagent grade.
 chemicals [or equivalent), unless otherwise
 specified. The reagents needed for analysis
 are as follows:
   &2.1  Calcium Oxide (CaO).  Certified
 grade containing 0.005  percent F or less.
   6.2-2  Pbenolphthalein Indicator.
 Dissolve 0.1 g of phenolphthalein in  a mixture
 of 50 ml of 00 percent ethanol end 50 ml
 deionized distilled water.
   6.2.3  Sodium Hydroxide (NaOH).
 Pellets.
   6.2.4  Sulfuric Acid {H.SO.).  Concentrated
   6.2J  Filters. Whatman No. 541, or
 equivalent
   6.2.6  Water. From same container as
 6.1.2 of Method 13A.
   6.2.7  Sodium Hydroxide. 5 M.  Dissolve
 20 g of NaOH in 100 ml of deionized distilled
 water.
   6.2.8  Sulfuric Acid. 25 percent (V/V).
 Mixl part of concentrated H.SO. with 3
 parts of deionized  distilled water.
              from  Federal  Register,  Vol.
   Friday,   Juno  20,  198TT
   'Mention of any trade name or ipeciFic product
 doet not constitute endorsement by the
 Environmental Protection Afency.

45,   Nox   121,   pp.   41857-41858,

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                                                                                 Section  No.  3.9.10
                                                                                 Revision  No.   0
                                                                                 Date  January  4,  1982
                                                                                 Page  2 of  2
                                                                              o
        Tola 1 Ionic Strength Adjustment
Duffer (TISAfi). .Place approximately 500 ml
of deionized distilled water In a 1-liter
toaker. Add 57 ml of glacial acetic acid. 58 g
of sodium chloride, and 4 g of cydohexylene
dinitrilo tetraacetic acid. Stir to dissolve.
Place the beaker in a water bath to cool iL
Clowly add 5 M NaOH to the solution.
neasuring the pH continuously with a
calibrated pH/referenca electrode pair, until
the pH is 5.3. Cool to room temperature. Pour
Into • 1-liter volumetric flask, and dilute to
volume with deionized distilled water.
Commercially prepared TISAB may be
substituted for the above.
  6.2.10  Fluoride Standard Solution. 0.1 M.
Oven dry some sodium fluoride (NaF) for a
minimum of 2 hours at 110'C, and store in a
desiccator. Then add 4.2 g of NaF to a 1-liter
volumetric flask, and add enough deionized
distilled water to dissolve. Dilute to volume
with deionixsd distilled water.

7. Procedure
  7.1  Sampling. Sample Recovery, and
Sample Preparation and Distillation.  Same
as Method 13A, Sections 7.1.7.2.  and 7.3.
respectively, except the notes concerning
chloride and sulfate interferences are not
applicable.
  72  Analysis.
  7.2.1- Containers No. 1 and No. 2.  Distill
suitable aliquots from Containers No. 1 and
No. 2. Dilute the distillate in the volumetric
flasks to exactly 250 ml with deionized
distilled water and mix thoroughly. Pipat a
23-ml aliquot from each of the distillate and
ttparate beakers. Add an equal volume of
TISAB. and mix. The sample should be at the
tame temperature as the calibration
standards when measurements are made. If
ambient laboratory temperature fluctuates
• more than ±2*C from the temperature at
which the calibration standards were
'manured, condition samples and standards
 in « constant-temperature bath before
 eaasurement. Stir the sample with a
 magnetic stirrer,during measurement to
 minimize electrode response time. If the
 stirrer generates enough heat to change
 solution temperature, place a piece of
 temperature insulating material such as cork,
 batween the stirrer and the beaker. Hold
 dilute samples (below io~4M fluoride ion.
 ccatsnt) in polyethylene beakers during
 c^turement
  Insert the fluoride and reference electrodes
into the solution. When a steady millivolt
reading is obtained, record it This may take
several minutes. Determine concentration
from the calibration curve. Between electrode
measurements, rinse the electrode with
distilled water.       .....:,
  723.  Container No. 3 (Silica Gel).  Same
as Method 13A, Section 7.4.2.    ,    ,

8. Calibration
  Maintain a laboratory log of all
calibrations.
  6.1  Sampling Train. Same as Method
13A.
  62   Fluoride Electrode. Prepare fluoride
standardizing solutions by serial dilution of
the 0.1 M fluoride standard solution. Pipst 10
ml of 0.1 M fluoride standard solution into a
100-ml  volumetric flask, and make up to the
mark with deionized distilled water for a 1CT1
M standard solution. Use  10 ml of 10"* M
solution to make a 10~*M solution tn the
same manner. Repeat  the  dilution procedure
and make 10" * and 10'* solutions.
  Pipet 50 ml of each standard into a
separate beaker. Add  50ml of TISAB to each
beaker. Place the electrode in the most dilute
standard solution. When a steady millivolt
reading is obtained, plot the value  on the
linear axis of semilog graph paper versus
concentration on the log axis. Plot  the
nominal value for concentration of the
standard on the log axis. e.g.. when 50 ml of
10" M standard is diluted with 50 ml of
TISAB. the concentration  is still designated
  Between measurements soak the fluoride
sensing electrode in deionized distilled water
for 30 seconds, and then remove and blot dry.
Analyze the standards going from dilute to
concentrated standards. A straight-line
calibration curve will be obtained, with
nominal concentrations of 10~4.W1, 10"*.
and 10"' fluoride molariry on the log axis
plotted versus electrode potential (in mv) on
the linear scale. Some electrodes may b«
slightly nonlinear between 10"' and 10~4M. If
this occurs, use additional standards between
these two concentrations.
i  Calibrate the fluoride electrode daily, and
check It hourly. Prepare fresh fluoride
standardizing solutions daily (10~*M or less).
Store fluoride standardizing solutions in
polyethylene or polypropylene containers.
(Note: Certain specific Ion meters have been
desisnsd specifically for fluoride electrode
use end give a direct readout of fluoride ion
concentration. These meters may b» used to
lien of calibration curves for fluoride
measurements over narrow concentration
ranges. Calibrate the meter according to the
manufacturer's instructions.)

ft Calculations
   Carry out calculations, retaining at least
one extra decimal figure beyond  that of the
acquired data. Round off figure* after final
calculation.
   0.1  Nomenclature.  Same as  Method 13^—v
Section 9.1. m addition:               /   A
M«F concentration from calibration curvV    )
     molarity.                          ^~^
   92  Average Dry Gas Meter Temperature
and Average Orifice Pressure Drop, Dry Gts
Volume. Volume of Water Vapor and
Moisture Content. Fluroide Concentration in
 Stack Gas, and Isokinetic Variation end
Acceptable Results.  Same as Method 13A.
Section 9.2 to 9.4,9.5.2, and 9.6. respectively.
   9.3  Fluoride in Sample.   Calculate the
 amount of F in the sample using the
 following:
                  Tf
              K   7T   (-V    M         Equation  13B-1
 Where:
 K-19mg/ml.

 10. References
   \. Same as Method 13A, Citations 1 and 2
 of Section 10.
   2. MacLeod. Kathryn E. and Howard L
 Criit Comparison of the SPADNS—
 Zirconium Lake and Specific Ion Electrode
 Methods of Fluoride Determination in Stack
 Emission Samples. Analytical Chemistry.
 *5:1272-1273.1973,
 tint Doe. W-ttIi» FiUd 4-lS-tS: fc«5 «a]
 cnjjxo coo! wio-01-u
                                                                                                                          O

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                                             Section No.  3.9.11
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 1 of 1
11.0  REFERENCES

     1.   Standards  of Performance  Promulgated  for  Five  Cate-
          gories of Sources in the Phosphate Fertilizer Industry.
          Federal Register, Vol. 42.   August 6,  1975.

     2.   Determination of Total Fluoride Emissions from Station-
          ary Sources;  Specific  Ion  Electrode Method.   Federal
          Register, Vol. 45.  June 20, 1980.

     3.   Martin,  R.  M.    Construction  Details  of  Isokinetic
          Source Sampling Equipment.  APTD-0581,  USEPA,  Air Pol-
          lution Control  Office, Research  Triangle Park,  North
          Carolina.  1971.

     4.   Rom,  J. J.  Maintenance, Calibration,  and Operation of
          Isokinetic  Source   Sampling  Equipment.    APTD-0576.
          USEPA Office  of Air Programs, Research Triangle Park,
          North Carolina.   1972.

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o
o
o

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                                             Section No. 3.9»12
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 1 of 22
12.0  DATA FORMS
     Blank data forms are provided on the following pages for the
convenience  of  the Handbook user.  Each blank  form  has  the cus-
tomary descriptive  title centered at the top of the page.   How-
ever, the section-page documentation in the top right-hand corner
of each page of other sections has been replaced with a number in
the lower right-hand corner that will enable the user to identify
ajnd  refer  to a  similar filled-in form in the text section.  For
example,  Form M13B-1.2  indicates that the  form  is Figure 1.2 in
Section  3.9.1  of the Method 13B Handbook.   Future  revisions of
this form,  if any, can be documented by 1.2A, 1.2B, etc.   Fifteen
of  the  blank forms  listed below  are  included  in this  section.
Three are  in the  Method Highlights Section  as shown by the MH
following  the  form  number  and  one  is left blank  in the  text.
  2.4A & B

  2.5

  2.6
  2.7
  3.1 (MH)
  4.1
  4.2
  4.3
  4.4
  4.5 (MH)
  5.1
     Title-
Procurement Log
Dry Gas Meter Calibration Data Form
(English and Metric units)
Posttest Meter Calibration Data Form
(English and Metric units)
Stack Temperature Sensor Calibration
Data Form
Nozzle Calibration Data Form
Fluoride Calibration Curve Data Form
Pretest Sampling Checks
Nomograph Data Form
Fluoride Field Data Form
Sample Recovery and Integrity Data Form
Sample Label
On-Site Measurement Checklist
Posttest Calibration Checks

-------
                                           Section No.  3.9.12
                                           Revision No. 0
                                           Date January 4,.1982
                                           Page 2 of 22                S~\
Form                     Title
5.2                 Fluoride Analytical Data Form
5.3                 Sample Analytical Data Form
5.4                 Expanded Calibration Curve Data Form
6.1A & 6.IB         Fluoride Calculation Data Form
                    (English, and Metric units)

8.2 (MH)            Method 13B Checklist To Be Used by Auditore
                                                                       o
                                                                        o
                                                              V*

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PROCUREMENT LOG
Item description

Quantity

Purchase
order
number


Vendor

Date
Ordered

Received

L Cost

Dispo-
sition

Comments

                      Quality Assurance Handbook M13A-1.2

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                                                                                  o
Date
                DRY GAS METER CALIBRATION DATA (English units)



                                            Meter box number
Barometric pressure, P,  =
                                   in. Hg   Calibrated by
Orifice
nanometer
setting
(AH),
in. H20
0.5
1.0
1.5
2.0
3.0
4.0
Gas volume
Wet test.
meter

ft3
5
5
10
10
10
10
Dry gas
meter
(vd),
ft3






Temperatures
Wet test
meter

-------
            METER BOX CALIBRATION DATA AND CALCULATION FORM (English units)

Nomenclature:

  V  = Gas volume passing through the wet test meter,  ft3.
   Vf

  V, = Gas volume passing through the dry gas meter, ft3.

  t  = Temperature of the gas in the wet test meter, °F.
   w

 t,  = Temperature of the inlet gas of the dry gas meter, °F.


 t,  = Temperature of the outlet gas of the dry gas meter, °F.
   o

  t , = Average temperature of gas in dry gas meter, obtained by average t,  and
       •»-     °ir                                                            i
       td ,  F.                                                           1
         o

  AH = Pressure differential across orifice, in. H2O.

  Y- = Ratio of accuracy of wet test meter to dry gas meter for each run; tolerance Y-  =
   x   Y10.02 Y,

   Y = Average ratio of accuracy of wet test meter  to dry gas meter for all six  runs;


AH@. = Orifice pressure differential at each flow rate  that gives 0.75 ft3/min of  air  at
       standard conditions for each calibration run, in. H2O; tolerance = AH@±0.15
       ( recommended) .

 AH@ = Average orifice pressure differential that gives 0.75  ft3/min of air at standard
       conditions for all six runs, in. H2O; tolerance  = 1.8410.25  (recommended).

   6 = Time  for each calibration run, min.

  P. = Barometric pressure, in. Hg.


                                        Quality Assurance Handbook 85-2. 3A  (backside)


-------
Date
DRY GAS METER CALIBRATION DATA (metric units)
                           Meter box number
Barometric pressure, P,  =
                  mm Hg    Calibrated by
o
Orifice
manometer
setting
(AH),
mm H20
10
25
40
50
75
100
Gas volume
Wet test
meter
 
-------
               METER BOX CALIBRATION DATA AND CALCULATION FORM (metric units)

   Nomenclature :

     V  = Gas volume passing through the wet test meter, m3 .
      Vr

     V, = Gas volume passing through the dry gas meter, m3 .

     t  = Temperature of the gas in the wet test meter, °C.
      w

     t ,  = Temperature of the inlet gas of the dry gas meter, °C.


     t^  = Temperature of the outlet gas of the dry gas meter, °C.
      o

     t, = Average temperature of gas in dry gas meter, obtained by average of t,  and
               °
                °
              ,
            o

      AH  = Pressure differential across orifice, mm H2O.

      Y.  = Ratio of accuracy of wet test meter to dry gas meter for each run;  tolerance Y.  =
          Y+0.02 Y.

       Y  = Average ratio of accuracy of wet test meter to dry gas meter for  all  six runs;


    AH@.  = Orifice pressure differential at each flow rate that gives 0.021  m3 of  air  at  standard
          conditions  for each calibration run, mm H2O; tolerance AH@. = AH§±3.8 mm H2O
          (recommended).

     AH@  = Average orifice pressure differential that gives 0.021 m3 of air  at standard con-
          ditions for all six runs, mm H2O; tolerance AH@ = 46.74 +6.3 mm H2O (recommended).

       8  = Time of each calibration run, min.

      P,  = Barometric  pressure, mm Hg.


O                       • '               '
                                           Quality Assurance Handbook M5-2.3B (backside)

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                           POSTTEST DRY GAS  METER  CALIBRATION DATA FORM (English  units)
      Test numbers
                       Date
Meter box number
Plant
      Barometric pressure, P,  =
                               in.  Hg   Dry gas meter number
                                  Pretest Y
Orifice
manometer
setting,
(All),
in. H20



Gas volume
Wet test
meter
>
°F



Dry gas meter
Inlet
(td),
i
OF



Outlet
Ctd ),
o
op



Average
(td),3
OF



Time
(9),
min



Vacuum
setting,
in. Hg




Y.
i



Y.
i
Vw Pb (td + 460)
V (P + M \(t + 460^
vd lpb + is.ejvw + *60/



Y =
If there  is only one thermometer on the dry gas neter, record the temperature under t, .
 V  = Gas volume passing through the wet test ceter, ft3.
 V, = Gas volume passing through the dry gas neter, ft3.
 t  = Tenperature of the gas in the wet test neter, °F.
t ,  = Temperature of the inlet gas of  the dry gas neter, °F.
t.  = Temperature of the outlet gas of the dry gas neter, °F.
  o
 t. = Average temperature of the gas in the dry gas neter, obtained by the  average of t,.  and t^
                                                                                     i       o
 All = Pressure differential across orifice, in. H20.
 Y. = Ratio of accuracy of wet test neter to dry gas ceter for each run.
  Y = Average ratio of accuracy of wet test meter to dry gas neter for all  three  runs;
      tolerance = pretest Y +0.05Y
 P, = Barometric pressure, in. Hg.
  6 = Time of calibration run, rain.
                                                            Quality Assurance Handbook M5-2.4A
                                                                                                         F.
O
                                             o
                                                        o

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                  POSTTEST HETER CALIBRATION DATA FORM  (Metric units)
Test numbers
Date
Meter box number
Plant
Barometric pressure, P. =
        nsa Hg   Dry gas meter number
                                 Pretest Y
Orifice
manometer
setting,
(AH),
mm H20



Gas volume
Wet test
meter
(vw),
m3
0.30
0.30
0.30
Dry gas
meter
,
in3



Temperature
Wet test
meter
(tw).
°C



Dry gas meter
Inlet

°C



Outlet
(td>.
0
°C



Average
(td),*
°C



Time
(e),
min



Vacuum
setting,
mm Hg




Yi



Yi
Vw Pb (td + 273)
Vd (Ph + AH Vlv; + 213\
d 1 b i3.6Aw ;



Y =
  If there is only one thermometer on the dry gas meter,  record  the temperature under t ..

   V  = Gas volume passing through the wet test meter,  in3.
    W
   V. = Gas volume  passing through the dry gas meter,  m3.

   t  = Temperature of  the gas in the wet test meter,  °C.
    W
  t.  = Temperature of  the inlet gas of the dry gas meter,  °C.
   di
  t.  = Temperature of  the outlet gas of the dry gas meter, °C.
    o
   t. = Average temperature  of the gas in the dry gas meter, obtained by the average of td  and td ,  °C.

   AH = Pressure differential across orifice, in H20.
   Y. = Ratio of accuracy of wet test meter to dry gas meter for each run.
    Y = Average ratio of accuracy of wet test meter to dry gas  raeter for all three runs;
        tolerance = pretest  Y +0.05Y

   P. = Barometric  pressure, in. Hg.

    6 = Time of calibration  run, min.
                                                            Quality Assurance Handbook M5-2.4B

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                                                                                   o
Date
 STACK TEMPERATURE SENSOR CALIBRATION DATA FORM

	  Thermocouple number 	
Ambient temperature

Calibrator
                'C  Barometric pressure
                                            in.  Hg
                    Reference:   mercury-in-glass

                     other
Reference
  point
 number
 Source
(specify)
 Reference
thermometer
temperature,
     °C
Thermocouple
potentiometer
temperature,
     °C
Temperature.
difference,
                                                                                    O
 Type of calibration system used.

 T(ref temp, °C + 273) - (test thermotn temp. °C + 273)1
  Lref temp, °C + 273J
                                                                                     O
                                          Quality Assurance Handbook M5-2.5

-------
                  NOZZLE CALIBRATION DATA FORM
Date
Calibrated by
Nozzle
identification
number

N
DI>
mm (in.)

o'zzle Diameter3
D2,
mm (in. )

D3,
mm (in. )

4D,b
mm (in. )

D C
avg

where:
         = three different nozzles diameters, mm (in.); each
           diameter must be within (0.025 mm) 0.001 in.


         = maximum difference between any two diameters, mm (in.),
           AD £(0.10 mm) 0.004 in.
    D    = average of DI; D2, and Dg.
                                Quality Assurance Handbook M5-2.6

-------
                        FLUORIDE CALIBRATION DATA FORM
                             LABORATORY WORKSHEET
Date standards prepared

Temperature of standards
                                                       Date
Electrode number
                                  o
Standard number






Control Sample
Concentration (M)
0.000001
0.00001
0.0001
0.001
0.01
0.1

Electrode potential (mV)







Note;  The concentration of the control sample determined from the calibration
curve must be between 0.002M and 0.01M.
                                                                                        O
Signature of analyst
Signature of reviewer
                                             Quality Assurance Handbook M5-2.7
                                  O
                                                                           !  i

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               NOMOGRAPH DATA FORM (English units)
Plant
Date
Sampling location
Calibrated pressure differential across
orifice, in. H2O
Average meter temperature (ambient + 20 °F), °F
Percent moisture in gas stream by volume, %
Barometric pressure at meter, in. Eg
Static pressure in stack, in. Eg
(P ±0.073 x stack gauge pressure, in. E2O)
Ratio of static pressure to meter pressure
Average stack temperature, °F
Average velocity head, in. B20
Maximum velocity head, in. B20
C factor
Calculated nozzle diameter, in.
Actual nozzle diameter, in.
Reference Ap, in. E2O
*H@
T
mavg
wo
Em
ps
P^m
Ts
avg
APavg
APmax

















                              Quality Assurance Handbook M5-4.1

-------
                                            PAHTICULATE FIELD  DATA
Plant
City
Location
Operator
Date
Run number
Stack dia.ii,

mm (in. )

                                  Meter calibration (Y)
                                  Pitot tube (C ) 	
                                  Probe length
                       Sheet
of
Sample box number
Meter box number
Meter AH@
Probe liner material
Probe heater setting
Ambient temperature
Barometric pressure (P. )
Assumed moisture
Static pressure (P )
C Factor
Reference AP
mm (in. ) Hg

mm (in. ) H20

mm (in. ) H20
                       Nozzle  identification number
                       Nozzle  diameter	 mm (in.
                       Thermometer number __^_^__^__^
                       Final leak rate      nrVnrin (cfm)
                       Vacuum  during leak check _^_^__
                                          	mm (in.) Hg
                       Filter position
                       Maximum AH 	
                       Remarks
Traverse
point
number














Sampling
time,
(0), min













Total
Clock
time,
(24 h)














Vacuum,
mm
(in.) Hg













Max
Stack
tempera-
ture
(T_),
°C(5F)













Avg
Velocity
head
(AP ),
mfn
(in.) H20














Pressure
differ-
ential
across
orifice
meter (AH),
mm
(in.) H20














Gas sample
volume (V ),
m3 (ft*)1"













Total
Gas sample temp-
erature at dry
gas meter
Inlet,
°C(°F)













Avg
Outlet,
°C(°F)













Avg
Temp
of gas
leaving
condenser
or last
impinger,
°C (8F)













Max
Filter
temp,
°C(°F)














                                                                                   Quality Assurance Handbook M5-4.2
   o
o
            o

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             SAMPLE RECOVERY AND INTEGRITY DATA FORM
Plant
Sample location 	
Sample recovery person
Sample date
       Run number
    Recovery date
                            MOISTURE
Impingers
Final volume (wt)
Initial volume (wt)
Net volume (wt)
     Total moisture
Color of silica gel
ml
ml
ml


(g)
(g)
(g)
g

Silica gel 	
Final wt
Initial wt
Net wt

g
g
g

g
g
g

ger water
                        RECOVERED SAMPLE
Water rinse and
impinger contents
container number
Water blank
container number
   Liquid level
   marked?
   Liquid level
   marked?
Samples stored and locked?
Remarks
Date of laboratory custody	
Laboratory personnel taking custody
Remarks
                              Quality Assurance Handbook M5-4.3
                                                                 /

-------
                                                         o
EXAMPLE OF A SAMPLE LABEL
Plant City
Site Sample type
'Date Run number
Front rinse D Front filter D Front solution D
Back rinse D Back filter D Back solution D
Solution Level marked
Volume: Initial Final J2
.__ -i .. ..„ , ^
Clean up by g
cc.



































                                                          O
                                                           o
                  Quality Assurance Handbook M5-4.4

-------
                   POSTTEST CALIBRATION CHECKS

Plant	  Calibrated by 	

Meter box number 	  Date	

Dry Gas Meter

Pretest calibration factor, Y 	^	 (within ±2%)
Posttest check, Y* 	(within ±5% of pretest)
Recalibration required?  	 yes	       no
  If yes, recalibration factor, Y 	       (within ±2%)
Lower calibration factor, Y  	for calculations (pretest or
  posttest)

Dry Gas Meter Thermometers

Was a pretest temperature correction used?  __i	 yes         no
  If yes, temperature correction 	 (within ±3°C (5.4°F) over
  range)
Posttest comparison with mercury-in-glass thermometer?* (within
  ±6°C (10.8°F) at ambient temperature)
Recalibration required?  	|	yes  	^       no
Recalibration temperature correction?~	(within ±3°C
  (5.4°F) over range)*
  If yes, no correction necessary for calculations if meter
  thermometer temperature is higher; if calibration temperature
  is higher, add correction to average meter temperature for
  calculations

Stack Temperature Sensor

Was a pretest temperature correction used?  	 yes  	 no
  If yes, temperature correction 	°C (°F) (within ±1.5% of
  readings in K (°R) over range)
Average stack temperature of compliance test,  T  	^K (°R)
Temperature of reference thermometer or solution for recalib'ra-
  tion 	K (°R)* (within ±10% of T )
Temperature of stack thermometer for recalibration 	K (°R)
Difference between reference and stack thermometer temperatures,
  AT  	K (°R)
Do values agree within ±1.5%?*  	 yes  	 no
  If yes, no correction necessary for calculations
  If no, calculations must be done twice—once with the recorded
  values and once with the average stack temperature corrected to
  correspond to the reference temperature differential  (AT ),
  both final result values must be reported since there is no way
  to determine which is correct


(continued)

                              Quality Assurance Handbook M5-5.1

-------
(continued)

Barometer

Was the pretest field barometer reading correct? 	 yes 	 no
Posttest comparison?* 	 mm (in.) Hg (±2.5 mm (0.1 in.) Hg)
Was calibration required?  	 yes  	  no
  If yes, no correction necessary for calculations when the field
  barometer has a lower reading; if the mercury-in-glass reading
  is lower, subtract the difference from the field data readings
  for the calculation
o
                                                                       o
*Moct nignificant items/parameters to be checked.
                                                                       O

-------
Plant
                                        FLUORIDE ANALYTICAL DATA SHEET
                                                      Date
                                yes
Sample location 	
Samples identifiable 	
Ambient temperature 	
Temperature of calibration  standards
Temperature of samples 	
                                                     Analyst
no  All liquid levels at marks
                                                      Constant  temperature  bath  used 	
                                                      Date  calibration  standards prepared
yes
 yes
no
no
Sample
number









Sample
identification
number









Total
volume of
sample,
(Vt), ml









Aliquot
total sam-
ple added
to still
(At), ml









Diluted
volume of
distillate
collected
(Vd), ml









Electrode
potential ,
mV









Concentration
of fluoride
from cali-
bration curve,
(M), molarity









Total
weight of
fluoride
in sample
(Ft), rag









Total weight of fluoride in sample (F.)
Ft =
Signature of analyst
                                                          Remarks:
Signature of reviewer or supervisor
                                                                           Quality Assurance Handbook H5-5.2

-------
                   EXPANDED CALIBRATION CURVE DATA FORM
                                    o
                          LABORATORY WORKSHEET
                                          Date
Date standards prepared _
Temperature of standards
Electrode number
Standard number
1
2
3
4
5
Control sample
Concentration, M
0.001
0.0005
0.0001
0.00005
0.00001

Electrode potential, mV






tote: The control sample, from the calibration curve, must be between
O002M and 0.0003M.
                                                                               O
Signature of analyst _
Signature of reviewer
                                         Quality Assurance Handbook M5-5.4
                                                                              O
                                                                   dy

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                  SAMPLE VOLUME  (ENGLISH UNITS)

                     , Tn	.  _ °R,  Pbar = __.__ in. Hg
Y = _ .	, AH = _  .	in.  H20

                     Pb  +  (AH/13.6)                  3
Vm(std) - 17-64 V mY -^-T-	" - - •	ft
                                                      Equation 6-1
                   FLUORIDE  CONTENT IN SAMPLE

V^ =             ml, A,_ =            ml,  V, =       .ml
 u   —• •"• ~~ ~~   ~~       U   •*•  ~~ •"•    ~"      Q   — «— —   —

M = _.	 M

               e V+. V -M                   f-
F^. = 4.19 x 10"D  ^. a =            x  10"° lb        Equation 6-4
            CONCENTRATION OF  FLUORIDE (ENGLIGH UNITS)

Vm(std) ' - -  •	ft3' Ft = - •	x  10"6 lb
          F^ =    .       x io"6  lb
           UD   —   — — —

           F  — F
c  =35.31 -~	^ =   .              Ib/dscf        Equation 6-5
 3          vm(std)
     All other equations same  as Methods  2  and 5.
                              Quality Assurance Handbook M5-6.1A

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                  SAMPLE VOLUME  (METRIC UNITS)



Vm = _ .	m3, Tm =	. _ -K, Pbar =	. _ nun Eg



Y = __.	, AH =	. _ mm H2O



                      Pb+ (AH/13.6)               3


Vm(std) = °-3858 Vm Y      Tm	 = -  •	m  Equation  6-1
                              Quality Assurance- Handbook M5-6.1B
o
                   FLUORIDE CONTENT  IN SAMPLE



Vt =	. _ml, At =	. _ml, Vd =	. jnl



M = _ .	M



        v  v                                                              S~\

F.  = 19 —r— M =           mg                       Equation 6-4        X_x
 t        rl_i_      ""   "*" ^ ™"
            CONCENTRATION OF FLUORIDE  (METRIC UNITS)




Vm(std) = - *	dscm' Ft = -  •	' Ftb = - *	



     Ft " Fth
C  = —	 =    .       mg/dscm                    Equation 6-5

 s    vm(std)   ~
     All other equations same as Methods  2  and 5.

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                                               Section No.  3 .1-0
                                               Revision No.  0
                                               Date  January 4,  1S62
                                               Page  1 of 7
                            Section 3.10

           METHOD 13A - DETERMINATION OF TOTAL FLUORIDE
                 EMISSIONS FROM STATIONARY SOURCES
                  (SPADNS Zirconium Lake Method)
                              OUTLINE
          Section.
Documentation
Number of
  pages
SUMMARY
(METHOD HIGHLIGHTS
METHOD DESCRIPTION
     1.   PROCUREMENT OF APPARATUS
          AND SUPPLIES
     2.   CALIBRATION OF APPARATUS
     3.   PRESAMPLING OPERATIONS
     4.   ON-SITE MEASUREMENTS
     5.   POSTSAMPLING OPERATIONS
     6.   CALCULATIONS
     7.   MAINTENANCE
     8.   AUDITING PROCEDURES
     9.   RECOMMENDED STANDARDS FOR
          ESTABLISHING TRACEABILITY
    10.   REFERENCE METHOD
    11.   REFERENCES
    12.   DATA FORMS
    3.10
    3.10
   2
   4
3.10.1
3.10.2
3.10.3
3.10.4
3.10.5
3.10.6
3.10.7
3.10.8
3.10.9
3.10.10
3.10.11
3.10.12
13
5
3
3
18
7
2
1
1
5
1
6

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Section No. 3.10
Revision No. 0
Date January 4, 1982
Page 2 of 7
                                                                   o
                      o
                             SUMMARY

     In Method  ISA,  total  fluorides (gaseous  and  particulate)
are extracted isokinetically from the source by using a sampling
train similar to  the  one specified in Method  5  (Section  3.4 of
this Handbook).   The filter is not required to be heated and may
be located immediately  after  the probe  or between the third and
fourth impinger.
     The SPADNS  zirconium lake colorimetric method for quantita-
tively measuring  the  fluorides  collected in the train is appli-
cable to fluoride (F)  emissions from stationary sources, but not
to fluorocarbons  such  as Freon.   The concentration range of the
method is from  0.05 to 1.4 pg F/ml; the method is applicable to
much higher concentration  by  using sample dilutions.  Sensitiv-
ity of the method has not been determined.
     An interferent in  the collection of fluorides is grease on
sample-exposed surfaces; due to adsorption the grease causes low
results.  If it can be shown to the satisfaction of the admini-
strator  that  samples  contain  only water  soluble  fluorides,
fusion and distillation may be omitted from the analysis.
     Interferences,  such  as  >300  rag  aluminium/2  and  >0.3 rog
silicon dioxide/£, prevent complete recovery of fluoride during
laboratory analysis, however, sample distillation will eliminate
this problem.  Chloride will distill over and  interfere with the
SPADNS zirconium  lake  color reaction.   This interference can be
prevented by adding silver sulfate  (5 mg of silver sulfate/mg of
chloride) into the distillation  flask.  However, if chloride ion
is present, use of specific-ion  electrode (Method 13B) is recom-
mended.   Sulfuric  acid carried  over during  distillation  will   ^^^
cause  a positive  interference;  to avoid the carryover, stop the   f  J
distillation  at  175°C  (347PF).   Residual  chlorine  will   also
interfere  with  this  colorimetric  method,  but  should  not be
present in the  type of  sample analyzed.

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                                             Section No. 3.10
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 3 of 7

     The color  obtained  when colorimetric reagent is mixed with
the sample  is  static for approximately 2 h.  After formation of
the color,  the  absorbances  of the sample and standard solutions
should be measured  at the same temperature.  A 3°C (5.4°F) dif-
ference between sample and  standard  solution temperatures will
produce an error of approximately 0.005 mg F/2.
     The method description which follows is based on the Refer-
ence Method1 that was promulgated on June 20, 1980.
     Section 3.10.10 contains a copy of the Reference Method and
blank data  forms  s.re provided in Section 3.10.12 for the conve-
nience of the Handbook user.
Note;   Due  to  similarities between  Method 13A  and  Method 13B
sampling  and  analytical  equipment  and procedures,  only  the
differences pertaining to  Method  13A will be  presented.   How.-
e\cer,   the   activity  matrices  are  all  included whether or not
differences occur in the written descriptions.  All other Method
ISA descriptions  will be referenced  to the  corresponding de-
scription in  Section  3.9,  Method 13B.   This is done  for both
time savings  to the reader  and cost  savings  to the Government.

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                                             Section No.  3.10
                                             Revision No. 0              ^^^
                                             Date January 4,  1982       f\
                                             Page 4 of 7                 V	J
                        METHOD HIGHLIGHTS

     Section 3.10  (Method  13A)  describes specifications for the
campling and analysis  of  total  fluoride emissions from station-
ary sources.  A  gas  sample is isokinetically extracted from the
cource stream, and the fluorides in the stream are collected in
the sampling train.
     The sampling train is similar to that in EPA Method 5, with
a  few  exceptions--the  filter does not have to be  heated and it
may be located either immediately after the probe or between the
third  and  fourth impingers.   If it is between the probe and the
first  impinger,  a borosilicate  glass  or stainless steel filter
holder with a 20-mesh  stainless steel screen filter support and        /*~"\
a  silicone rubber gasket  must  be used.   If it is  between the        V_y
third  and  fourth impingers,  a glass  frit  filter  support may be
used.
     Sampling is generally the same as in Method 5, but a nozzle
size that will maintain an isokinetic sampling rate of <28 £/min
(<1.0  ft3/min) must  be used.  Samples and standards must be the
came temperature  during analysis by the colorimetric method.  A
change of 3°C (5.4°F) will cause an error of 0.005 mg F/£ in the
sample measurements.  Distillation  during sample  analysis has
been found to be the main cause of error in this method.
     The collected sample  is recovered by transferring the mea-
sured  condensate  and   impinger water  to  a sample  container,
adding the filter and the  rinsings of  all  sample-exposed sur-
faces  to  this container,   and  fusing and  distilling  the sample
for  colorimetric  analysis.   Fusion  and  distillation  may  be
omitted if it can be shown  to  the  satisfaction  of the adminis-
trator that the  samples  contain only water  soluble fluorides.        ()
     Results of  collaborative tests2  show that fluoride concen-        —^
trations from 0.1 to 1.4 mg F/m3 could be determined with an in-
tralaboratory precision of 0.044 mg F/m3 and an inter laboratory    /'?/•"

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                                             Section No. 3.10
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 5 of 7

precision of 0.064 rag F/m3.  Six contractors each simultaneously
took duplicate  samples from the  stack.   The collaborative test
did not find any bias in the analytical method.2
     The Method Description (Sections 3.10.1 to 3.10.9) is based
on the detailed  specifications  in the Reference Method (Section
3.10.10) promulgated by EPA on June 20, 1980.x
     The appropriate  blank data forms at the  end  of the Method
Highlights Section  of Method '13B  (Section  3.9) may  be removed
from the Handbook and used  in  the pretest,  test,  and posttest
operations.  Each form has  a  subtitle  to  assist  the user in
finding a  similar filled-in  form in the method description.  On
the blank  and  filled-in  forms,  the  items/parameters  that can
cause  the  most  significant  errors are  designated with  an as-
terisk.
1.,   Procurement of Apparatus and Supplies
     Section 3.10.1  (Procurement  of  Apparatus  and  Supplies)
gives  specifications,   criteria,  and  design  features for the
required equipment and materials.   The  sampling  apparatus for
Method  13A has  the  same  design  features  as that of Method 5,
except for the  positioning of the filter in the sampling train.
This section can be  used  as a guide for procurement and initial
checks  of  equipment and  supplies.   The  activity  matrix (Table
1.1) at the end of the section is a summary of the details given
in the text and can be used as a quick reference.
2.   Pretest Preparations
     Section 3.10.2  (Calibration  of  Apparatus)  describes the
required  calibration  procedures  for the  Method 13A sampling
equipment  (same* as Method 13B)  for the  colorimetric method.  A
pretest  checklist  (Figure  3.1  in  Section  3.9.3  or  a similar
form)  should be used  to summarize  the calibration  and other
pertinent pretest data.
     Section 3.10.3  (Presampling Operations)  is the same as for
Method 13B.

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o
                                             Section No.  3.10
                                             Revision No. 0
 ;                                            Date January 4,  1982
                                             Page 6 of 7

     Activity matrices for the  calibration of equipment and the
presampling operations (Tables 2.1 and 3.1) summarize the activ-
ities.
3V   On-site Measurements
     Section 3.10.4  (On-Site  Measurements) describes procedures
for  sampling and sample  recovery and is the  same  as for Method
13B.
4.   Posttest Operations
     Section  3.10.5   (Postsampling  Operation)   describes  the
postsampling  activities  for  checking  the  equipment  and  the
analytical procedures.  A  form is given for recording data from
the  posttest  equipment calibration checks;  a copy  of the form
should be included in the emission test final report.  A control
sample  of known (F)  concentration  should be  analyzed before     C  J
analyzing the sample  for a quality control check on the analyt-
ical  procedures.   The  detailed analytical  procedures  can be
removed for use  as easy references in the  laboratory.  An activ-
ity  matrix  (Table 5.1)  summarizes  the postsampling operations.
     Section   3.10.6  (Calculations)   describes  calculations,
nomenclature, and significant digits  for  the data reduction.  A
programmed  calculator  is  recommended  to  reduce  calculation
errors.
     Section 3.10.7  (Maintenance) recommends routine and preven-
tive  maintenance programs.   The  programs  are not required, but
their use should reduce equipment downtime.
5.   Auditing Procedures
     Section  3.J.0.8  describes performance  and  system  audits.
Performance  audits  for both  the analytical phase  and the  data
processing  are   described.  A checklist (Figure 8.2)  outlines  a      ^_^^
recommended system audit.                                             \)
      Section  3.10.9  lists  the  primary  standards to  which the
working  standards or calibration standards should be  traceable.

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                                             Section No. 3.10
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 7 of 7
6.   References
     Section 3.10.10 contains  the  promulgated Reference Method;
Section  3.10.11 contains  the  references  cited  throughout  the
text; and  Section  3.10.12 either  contains  copies of data formo
recommended  for Method 13A or references  the user  to forms in
Method 13B.

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o
o
o

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                                             Section No. 3.10.1
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 1 of 13
                       METHOD DESCRIPTION

1.0  PROCUREMENT OF APPARATUS AND SUPPLIES
     A  schematic  of  the  sampling  train used  in Method  13  is
shown in Figure 1.1.   The train and the sampling procedures are
similar  to  EPA Method  5;  the  procedures  and equipment  for
Methods  13A and 13B  are  identical.   Commercial models  of the
train  are  available.    For those who  want to build  their own,
construction details  are  in  APTD-0581;3 allowable modifications
are described therein.  The operating, maintenance,  and calibra-
tion procedures for the sampling train are in APTD-0576.4  Since
correct usage is important in obtaining valid results, all users
are advised to read  that document and  to  adopt its procedures
unless alternatives are outlined therein.
     Specifications,  criteria,  and/or  design  features are given
in  this  section to aid  in  the  selection of equipment  or any
components  that are   different  from  those  in  Section  3.9.1.
Procedures  and limits  (where applicable)  for acceptance checks
are also given.
     Table 1.1 at the end of this section summarizes the quality
assurance  activities  for the   procurement  and acceptance  of
apparatus and supplies.
1.1  Miscellaneous  Glassware
1.1.1  Pipettes - Several volumetric pipettes (Class A)—includ-
                                    >•)
ing 2, 4, 5, 6, 8,  10,  12, 14, 20, 25, 50 mi's—should be avail-
able.  Record  the  stock numbers, and visually check for cracks,
breaks,  or  manufacturer's flaws.   If  irregularities are found,
either replace or return to the supplier.
1.1.2  Volumetric Flask - Several glass volumetric flasks, Class
A,  (50-ml,  100-ml, 250-ml,  1000-ml)  are  needed to  dilute the
sample and to prepare standards and agents.

-------
  1.9-2.5 on
(0.75-1.0 in.)
1.8 cm{0.75 In.)

     PITOT TUBE
TEMPERATURE
  SENSOR         ,
            PROBE ,
                 I
                 I
                DF
            .   OPTIONAL
            TILTER HOLDER"

STACK HALL   L J:?f?Ii°!L J FILTER HOLDER
     /
            PROBE
         TYPE S    C
       PITOT TUBE
                                                                        THERMOMETER
                                                                               CHECK
                                                                                ALVE
                             PITOT
                           MANOMETER
                                  IMPINGERS
                           THERMOMETERS
                                                      BY-PASS   KAIH
                                                       VALVE   VALVE WGAUGE
                      ORIFICE
                     MANOMETER
                                    AIR TIGHT
                                      PUMP
                                        DRY TEST
                                          METER
                                                     VACUUM
                                                      LINE
                                                                            *xJ U £d to
                                                                            iQ r*" < o
                                                                                W H-
                                                                            NJQ H-O
                                                                              O' O 3
                                                                            osa~
                                                                                O •
                       Figure 1.1.   Fluoride sampling train.
                                                                                                  CO
                                                                                                  M
   o
                         o
                                                                            o

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                                             Section No. 3.10.1
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 3 of 13

1.1.3   Erlenmeyer Flask or Plastic Bottle  -  A 500-ml Erlenmeyer
flask or plastic bottle  is  needed to store the SPADNS solution.
1.2  Reagents and Supplies (Sample Recovery and Analysis)
     Unless  otherwise indicated,  all  reagents should  meet the
specifications  of  the Committee  on  Analytical Reagents  of the
American Chemical Society  (ACS);  otherwise,  use the best avail-
able grade.
1.2.1   Calcium Oxide  (CaO) -  A reagent grade 'or a certified ACS
grade of CaO containing <_0.005% F is needed.
1.2.2  Filters - Whatman No.  541 (or equivalent) filters are re-
quired  for filtration of the  impinger  contents and recovery of
the sample.
1.2.3   Hydrochloric Acid (HC1) - An  ACS  reagent  grade  or the
equivalent concentrated HC1 is needed.
1.2.4   Phenolphthalein Indicator  - A reagent  grade or  a certi-
fied  ACS   0.1%  phenolphthalein  should be  a  1:1  ethanol-water
mixture.
1.2.5   Silver Sulfate (AggS04) -  An  ACS  reagent  grade  or the
equivalent Ag2SO4 should be used.
1.2.6  Sodium Hydroxide (NaOH) Pellets - An ACS reagent grade or
the equivalent is needed,
1.2.7    Sodium  Fluoride (NaF) Standard   -  Dissolve   0.2210 g
±0.0005 g  of reagent grade NaF in deionized distilled water and
dilute  to  1000  ml.    Dilute  100 ml of  this  solution to 1000 ml
with distilled  water; 0.01 mg F/ml  water.  NaF should be oven
dried at 110°C for at least 2 h prior to weighing.
1.2.8   Sulfuric Acid (Hj>S04)   - An  ACS  reagent  grade  or  the
equivalent concentrated H2SO4  is needed.
1.2.9   Sulfuric Acid, 25 Percent (v/v)  -  Cautiously add  1 part
of  concentrated H2S04  to 3   parts  deionized  distilled  water.

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                                             Section No.  3.10.1
                                             Revision No. 0           /*~"\
                                             Date January 4,  1982     I )
                                             Page 4 of 13

1.2.10  Water - Deionized distilled water needed as specified in
Table 1.1 at the end of this section and in Section 3.9.1.
1.2.11  SPADNS Solution - Dissolve 0.960 ±0.010 g of SPADNS rea-
gent  4,5  dihydroxy-3-(parasulfophenylazo)-2,7-naphthalenedisul-
fonic  acid  trisodium  salt  (also  called  sodium-2-(parasulfo-
phenylazo)-l,8-dihydroxy-3,6-naphthalenedisulfonate)   in   dis-
tilled  water, and  dilute  to  500  ml.   This diluted  solution is
stable for about 1 mo if stored in a sealed bottle and protected
from direct sunlight.
1.6.12  Reference Solution - Add 10 ml of the SPADNS solution to
100 ml  distilled water.  Dilute 7 ml of  concentrated HC1 to 10
ml; then add the diluted HC1 to the diluted SPADNS.  This refer-
ence solution, which is needed to set the spectrophotometer zero
point, is stable for at least 2 mo.                                    \   }
1.2.13  SPADNS Mixed Reagent  (ZrOCl? • 8H?O + HCl Mixed with
SPADNS Solution)  - First  prepare the zirconyl-acid  reagent by
dissolving  0.135  ±0.005  g  of  zirconyl  chloride  octahydrate
(ZrOCl2'8H20)  in 25  ml of distilled water.  Then  add 350 ml of
concentrated  HCl,  and  dilute to  500  ml with  distilled water.
Next,  prepare  the SPADNS  mixed  reagent  (acid zirconyl-SPADNS
solution) by  combining  equal  volumes  of the SPADNS solution and
the zirconyl-acid reagent.  The mixed reagent will be stable for
at least 2 mo.
     Check  all  reagents  for  grades  and  ACS  certifications.
Replace or return to the manufacturer any reagent which does not
meet the standards.
1.3  Analytical Equipment
               •
1.3.1  Bunsen Burner - A Bunsen burner capable of distilling 200
ml in <15 min is required to heat the boiling flasks.
1.3.2   Crucible - A  nickel crucible  with  a  capacity of 75 to
100 ml is needed to evaporate the water from the sample on a hot
plate.

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                                             Section No. 3.10.1
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 5 of 13

     Upon  receipt,  check  for  cracks or manufacturing  flaws  as
well as  for capacity.   If it does  not  meet specifications  re-
place or return it to the manufacturer.
1.3.3  Hot Plate  - A  hot plate capable  of  500°C  (932°F) is  re-
quired for heating the sample in a nickel crucible.
     Check  upon  receipt and before  each use for  damage.  Check
the heating capacity against a mercury-in-glass thermometer.   If
inadequate,  repair or  return  the  hot  plate  to  the  supplier.
1.3.4   Electric  Muffle  Furnace - An  electric  muffle  furnace
capable of  heating to  600°C (1112°F) is needed to fuse the sam-
ple.
     Check the heating capacity against a mercury-in-glass ther-
mometer.    Replace or  return to the  manufacturer  any unit which
does not meet specifications.
1^3.5  Balance -  A balance with a  capacity of 300  g  ±0.5 g is
needed to determine moisture.
     Check  for damage  against  a series of standard weights upon
receipt and before each  use.   Replace or return to the manufac-
turer if damaged or if it does not meet specifications.
1.3.6  Analytical Balance - An  analytical   balance  capable  of
weighing to within 0.1 mg is needed for preparation of the stan-
dard fluoride  solution and the analytical  reagents.  Check the
balance frequently with Class S weights.
1.3.7  Constant Temperature Bath  -  For  optimum  measurement  of
the sample  concentration,  a water bath  is  needed to maintain a
constant room  temperature.  This bath must maintain a constant
temperature of ±1°C (1.8°F) in the room temperature range.
     Check upon* receipt  and before  each use for damage and tem-
perature constancy.
1.3.8  Spectrophotometer  - A spectrophotometer is required  for
determining the  absorbance of  the  sample  and the  calibration
ctandards  at  a wavelength of 570 nanometers using a 1-cm path-
length.
                                                     's,

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                                             Section Ho. 3.10.1
                                             Revision No. 0         ><->.
                                             Date January 4, 1982   (   )
                                             Page 6 of 13           ^-s

     Check  the spectrophotometer  upon receipt  and  before each
uce for proper operation according to the manufacturer's manual.
1.3.9  Spectrophotometer Cells  -  Glass cuvettes with 1-cm path-
length are  required to contain sample and  standards during the
cbsorbance measurements.  Check upon receipt and before each use
for cracks or scratches on optical surfaces.  Replace the cuvet-
tcc necessary.
                                                                   o
                                                                   o

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                                                       Section  No. 3.10.1
                                                       Revision No.  0
                                                       Date January  4,  1982
                                                       Page 7 of 13
            TABLE 1.1.   ACTIVITY MATRIX  FOR  PROCUREMENT OF APPARATUS
                                  AND  SUPPLIES
Apparatus
Sampling

Probe liner
Probe nozzle
Pi tot tube
Differential
  pressure
  gauge (in-
  clined ma-
  nometer)
Filters
(continued)
Acceptance limits
Specified material of
construction; equipped
with heating system
capable of maintaining
120°±14°C (248° ±25°F)
at the exit
Stainless steel (316)
with sharp, tapered
angle <30°; differ-
ence in measured diam-
eters £0.1 mm (0.004
in.); no nicks, dents,
or corrosion
Type S (Meth 2, Sec
3.1.2); attached to
probe with impact
(high pressure) opening
plane even with or
above nozzle entry
plane
Meets criteria (Sec
3.1.2); agrees within
5% of gauge-oil
manometer
Capable of withstand-
ing temperatures to
135°C (275°F), 95%
collection efficiency
for 0.3 urn particles,
low F blank (<0.015
mg F/cm2)
Frequency and method
   of measurements
Visually check the
probe and run the
heating system
Visually check upon
receipt and before
each test; use a mi-
crometer to measure
ID before field use
after each repair
Visually check for
vertical and hori-
zontal tip alignments;
check the configura-
tion and the clear-
ances; calibrate
(Sec 3.9.2)
Check against a gauge-
oil manometer at a
minimum of three
points:  0.64(0.025);
12.7 (0.5); 25.4(1.0)
mm (in.) H20
Check each batch for
F blank values,
visibly inspect for
pin holes or flaws
Action if
requirements
are not met .
Repair, return
to supplier,
or reject
Reshape and
sharpen, re-
turn to the
supplier, or
reject
Repair or re-
turn to sup-
plier
As above
Reject batch

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                                                       Section No.  3.10.1
                                                       Revision No.  0
                                                       Date  January 4, 1982/-N.
                                                       Page  8  of 13          (]
TABLE 1.1 (continued)
Apparatus
Acceptance limits
Frequency and method
   of measurements
Action if
requirements
are not met
Filter holder
Leak free;  borosilicate
glass
Visually check before
use
Return to
supplier
Condenser
Four impingers,  standard
stock glass; pressure
drop not excessive
Visually check upon
receipt; check pres-
sure drop
As above
Vacuum gauge
0-760 mm (0-30 in.)  Hg,
±25 mm (1 in.) at
380 mm (15 in.) Hg
Check against mer-
cury U-tube manometer
upon receipt
Adjust or re-
turn to sup-
plier
Vacuum pump
Leak free; capable of
maintaining flow rate
of 0.02-0.03 mVmin
(0.7 to 1.1 ftVmin)
for pump inlet vacuum
of 380 mm (15 in.) Hg
Check upon receipt
for leaks and capaci-
ty
Repair or re-
turn to sup-
plier
                                                                              o
Barometer
Capable of measuring
atmospheric pressure
±2.5 mm (0.1 in.) Hg
Check against a mer-
cury- in- glass barom-
eter or equivalent;
calibrate (Sec 3.1.2)
Determine cor-
rection fac-
tor, or reject
if difference
more than ±2.5
mm (0.1 in.)
Hg
Orifice meter
AH@ of 46.74± 6.35 mm
(1.84 ± 0.25 in.) H20
at 20°C (68°F);
optional
Upon receipt, visual-
ly check for damage;
calibrate against wet
test meter
Repair or re-
turn to sup-
plier
Dry gas meter
Capable of measuring
volume within ±2% at a
flow rate of 0.02
mVrain (0.7 ftVmin)
Check for damage upon
receipt and calibrate
(Sec 3.9.2) against
wet test meter
Reject if dam-
aged, behaves
erratically,
or cannot be
properly ad-
justed
                                                                               O
 (continued)

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                                                       Section  No. 3.10.1
                                                       Revision No.  0
                                                       Date January  4,  1982
                                                       Page 9 of 13
TABLE 1.1 (continued)
Apparatus
Thermometers
Sample Recovery

Probe liner and
  probe nozzle
  brushes
Wash bottles
Storage con-
  tainer
Graduated
  cylinder
Funnel
Rubber police-
  man
Acceptance limits
±1°C (2°F) of true
value in the range of
0° to 25°C (32° to 77°F)
for impinger thermometer
and ±3°C (5.4°F) of true
value in the range of
0°C to 90°C (32° to
194°F) for dry gas
meter thermometers
Nylon bristles with
stainless steel han-
dles; properly sized
and shaped
Polyethylene or glass,
500 ml
High-density polyeth-
ylene, 1000 ml
Glass, Class A, 250 ml
Glass, diameter 100 mm;
steo length 100 mm
Properly sized
 Frequency and method
   of measurements
Check upon receipt
for dents or bent
stem, and calibrate
(Sec 3.9.2) against
mercury-in-glass
thermometer
Visually check for
damage  upon receipt
Visually check for
damage  upon receipt
 Visually check for
 damage  upon receipt;
 be  sure caps make
 proper  seals
 Upon  receipt, check
 for stock  number,
 cracks, breaks, and
 manufacturer flaws
 Visually check for
 damage  upon  receipt
 Visually  check for
.damage  upon  receipt
Action if
requirements
are not met
Reject if un-
able to cali-
brate
Replace or re-
turn to sup-
plier
As above
As above
As above
As above
As above
(continued)

-------
                                                       Section Mo.  3.10.1
                                                       Revision No. 0
                                                       Date  January 4,  1982
                                                       Page  10 of 13
                                                                  o
TABLE 1.1 (continued)
Apparatus
Pipettes,  volu-
  metric flask,
  beaker,  flask
  adapter, con-
  denser,  con-
  nection  tube,
  Erlenmeyer
  flask
Distillation
Apparatus

Bunsen burner
Crucible
Analytical
Equipment

Hot plate
Electric muffle
  furnace
Acceptance limits
Glass, Class A
Capable of distilling
220 ml in <15 min
Nickel material;  75-
100 ml
Heating capacity of
500°C (932°F>
Heating capacity of
600?C
Frequency and method
   of measurements
Upon receipt, check
for stock number,
cracks, breaks and
manufacturer flaws
Visually check upon
receipt; check heat-
Ing capacity, check
for damage
Check upon receipt
for cracks or flaws
Check upon receipt
and before each use
for damage; check
heating capacity
against mercury-in-
glass thermometer
Check upon receipt
and before each use
for damage; check
heating capacity
upon receipt against
mercury-in-glass
thermometer
Action if
requirements
are not met
Replace or re-
turn to sup-
plier
Replace or re-
turn to manu-
facturer
                                                                                   O
Replace or re-
turn to manu-
facturer
Replace or re-
turn to manu-
facturer
Replace or re-
turn to manu-
facturer
                                                                                   O
(continued)

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                                                       Section No. 3.10.1
                                                       Revision  No. 0
                                                       Date January 4,  1982
                                                       Page 11 of 13
TABLE 1.1 (continued)
Apparatus
Balance
Water bath
Spectropho-
  tometer
Reagents

Filters
Silica gel
Distilled water
Crushed ice
Stopcock grease
Acceptance limits
Capacity of 300 g ±0.5g
Capable of maintaining
constant room tempera-
ture
Capable of measuring
absorbance at 570 nm
and providing >1 cm
light path    "
Whatman No.
equivalent
            541 or
Indicating Type 6-16
mesh
Must conform to ASTM-
D1193-74, Type 3
Acetone insoluble, and
heat stable silicon
grease
                         Frequency  and method
                            of measurements
                         Check  for  damage and
                         against  ser-ies of
                         standard weights upon
                         receipt  and  before
                         each use
                         Check with mercury-
                         in-glass  thermometer
                         Check upon  receipt
                         and before  each  use
                         for damage;  see  manu-
                         facturers'  operating
                         manual
Visually check for
damage upon receipt
                         Upon receipt check
                         label  for grade  or
                         certification"
                         Check each riot
                         Check frozen condition
Upon receipt, check
label for grade or
certification
                       Action  if
                       requirements
                       are  not met
                       Replace or  re-
                       turn to manu-
                       facturer
                       Repair
                       Replace  or  re-
                       turn  to  manu-
                       facturer
Replace or re-
turn to sup-
plier
                       Replace  or re-
                       turn to  manu-
                       facturer
                       Replace  or re-
                       turn  to  manu-
                       facturer
                                               As above
(continued)

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                                                 Section No.  3.10.1
                                                 Revision No.  0
                                                 Date January 4,  1982
                                                 Page 12 of 13
o
TABLE 1.1 (continued)
Apparatus
Reagents
Calcium oxide
powder
Phenolphthalein
Sodium hy-
droxide
Sulfuric acid
Silver sulfate
powder
Hydrochloric
acid
Sodium fluoride
solution
SPADNS solu-
tion
Acceptance limits
Reagent grade or cer-
tified ACS
0.1% in 1:1 ethanol-
water mixture; reagent
grade or certified ACS
NaOH pellet, 5M NaOH
reagent grade or cer-
tified ACS
Concentrated, reagent
grade or certified ACS;
25% (v/v) reagent grade
or ACS
Reagent grade or certi-
fied ACS
Concentrated, reagent
grade or certified ACS
0.01 mg F/ml , reagent
grade or certified ACS
Dissolve 0.960 + 0.010
g of SPADNS reagent,
4,5-dihydroxy-3-(p-
sulfophenylazo)-2,7-
naphthal enedi sul f oni c
acid trisodium salt,
reagent grade or cer-
tified ACS
Frequency and method
of measurements
As above
As above
As above
As above
Upon receipt, check
label for grade or
certification
As above
As above
As above
Action if
requirements
are not met
As above
As above
As above
As above
Replace or re-
turn to manu-
facturer
As above
As above
As above
                                                                          O
                                                                          o
(continued)

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                                                       Section Ho.  3.10.1
                                                       Revision No.  0
                                                       Date January 4, 1982
                                                       Page 13 of 13
TABLE 1.1 (continued)
Apparatus
Reference
  solution
SPADNS mixed
  reagent
Acceptance limits
Add 10 ml SPADNS solu-
tion to 100 ml  dis-
tilled water;  dilute
7 ml cone HC1  to 10
ml with distilled
water; add to  diluted
SPADNS solution; rea-
gent grade or  certi-
fied ACS
Dissolve 0.135 + 0.005
g [ZrOCV8H20] in 25
ml distilled water; add
350 ml cone HC1; dilute
to 500 ml with distilled
water; mix equal volumes
of SPADNS solution and
the above zirconyl acid
reagent; reagent grade
or certified ACS
Frequency and method
   of measurements
As above
As above
Action if
requirements
are not met
As above
As above

-------
o
o
o

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                                             Section No. 3.10.2
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 1 of 5
2.0  CALIBRATION OF APPARATUS
     Calibration of apparatus is one of the most important func-
tions  in maintaining  data  quality.   The detailed  calibration
procedures included in  this  section are designed for the equip-
ment  specified in  Method  13A and  described  in the  previous
section  (Section  3.9.2).  A laboratory  log  book of  all  cali-
brations  must be  maintained.   Table  2.1  at  the  end  of  thio
section  summarizes  the  quality assurance activities  for  cali-
bration.  This section is the same as Method 13B (Section 3.9.2)
with  the  exception of  the calibration  of the spectrophotometer
as detailed below.
2.1  Spectrophotometer
     An  initial calibration curve should be  made to  check the
operation of  the  spectrophotometer.  Conduct the check as  fol-
lows :
     1.   Prepare the  blank standard by  adding 10 ml  of SPADNS
mixed reagent to 50 ml of distilled water.
     2.   Pipette 2.0, 4.0, 6.0, 8.0, 10.0, 12.0, and 14.0 ml of
the  standard  fluoride  working solution  into   separate 100-ml
volumetric  flasks.   Dilute  to the  mark  with  distilled water.
     3.   Pipette  50  ml of  each  dilution into 100-ml beakers;
then pipette  10.0 ml  of SPADNS mixed reagent into each and mix.
These standards will  contain 0, 10,  20,  30, 40,  50,  60, and 70
pg F> respectively.
     4.   Place the reference  standards  and the reference solu-
tion  in a constant temperature bath for  30  min before reading
the  absorbances  with  the  spectrophotometer.   The bath must be
within ±3°C (5.4°F) of ambient temperature.
     5.   Set the spectrophotometer at 570 nm and use the refer-
ence solution to set at  zero absorbance.
     6.   Determine  the absorbance  of  the standards.   Record
data on the standard data form as shown in Figure 2.1.

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                                                    Section No.  3.10.2
                                                    Revision No.  0
                                                    Date January 4,  1982
                                                    Page 2 of 5
                                                                                  O
Spectrophptometer number	

Calibration date	^f J/3/$O
                                                    Analyst  £. 
-------
                                             Section No. 3.10.2
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 3 of 5

     7.   The wavelength calibration should be checked initially
and yearly  thereafter.   This can be done  using  a didymium fil-
ter.  See  suppliers  instructions  for  its  use.   The  wavelength
should agree within  ±10  nm.   If not, contact the manufacturer's
representative for adjustment.

-------
                                                      Section  No. 3.10.2
                                                      Revision No.  0
                                                      Date January  4,  1982
                                                      Page 4 of 5
                                                                   o
         TABLE 2.1.   ACTIVITY  MATRIX  FOR CALIBRATION OF EQUIPMENT
Apparatus
Wet test meter
Dry gas meter
Thermometers
Barometer
Probe nozzle
(continued)
Acceptance limits
Capacity of >3.4 mVh
(120 ftVh) ;~accuracy
within ±1.0%
Y. = Y ± 0.02 Y at
flow rate of 0.02 -
0.03 mVmin (0.7 -
1.1 ftVmin)
Impinger thermometer
±1°C (2bF); dry gas
meter thermometer
+3°C (5.4°F) over
applicable range
+2.5 -mm (0.1 in.) Hg of
mercury-in-glass barom-
eter
Average three ID mea-
surements of nozzle;
difference between high
and low <0.1 mm
(0.004 in.)
Frequency and method
    of measurement
Calibrate initially
and yearly by liquid
displacement
Calibrate with wet
test meter initially
to agree within Y ±
0.02 Y and when post-
test check is not
within Y ± 0.05 Y
Calibrate each ini-
tially against a
mercury-in-glass
thermometer; before
field trip compare
each with mercury-
in-glass thermometer
Calibrate initially
vs mercury-in-glass
barometer; check
before and after
each field test
Use a micrometer to
measure to near-
est 0.025 mm (0.001
in.)
Action if
requirements
are not met
Adjust to
meet specifi-
cations, or
return to
manufacturer
Repair or re-
place, and
then recali-
brate
Adjust, de-
termine a
constant cor-
rection fac-
tor, or re-
ject
Adjust to
agree with
certified
barometer
Recalibrate,
reshape, and
sharpen when
nozzle be-
comes nicked,
dented, or
corroded
                                                                                   O
                                                                                   o
                                                                          (.

-------
                                                      Section Ho.  3.10.2
                                                      Revision No.  0
                                                      Date January 4, 1982
                                                      Page 5  of 5
TABLE 2.1 (continued)
Apparatus
Stack tempera-
  ture sensor
Trip balance
Pitot tube
Spectrophotom-
  eter
Wavelength
Acceptance limits
±1.5% of average abso-
lute stack temperature,
°R
Standard Class-S
weights within ±0.5 g
of stated value
Type S; initially
calibrated according to
Section 3.1, Meth 2;
tube tips undamaged
Standard solutions
agree within ±2% of
calibration curve
±10 nm
Frequency and method
    of measurement
Calibrate initially;
check after each
field test
Verify calibration
when first purchased,
any time moved or
subject to rough
handling, and during
routine operations
when not within
± 0.5 g
Visually check
before each field
test
Check standard solu-
tions for each test;
new calibration curve
made when standards
do not agree within
±2% of existing curve
or when SPADNS mixed
reagent is newly made
Yearly
Action if
requirements
are not met
Adjust or
reject
Have the
manufacturer
recalibrate
or adjust
Repair or
replace
Make new rea-
gents and
calibration
curve
Contact manu-
facturer 's
representa-
tive for
adjustment

-------
o
o
o

-------
                                             Section Ho. 3.10.3
                                             Revision No. 0
                                             Date  January 4, 1982
                                             Page  1 of 3
3.0  PRESAMPLING OPERATIONS
     The quality assurance activities  for presampling operations
are summarized in Table 3.1.   See  Section 3.0,  of this Handbook
for details  on preliminary  site visits.   This section  is the
same as Method 13B (Section 3.9.3).
                                                &•

-------
                                                       Section No.  3.10.3
                                                       Revision No.  0
                                                       Date January 4, 1982
                                                       Page 2  of 3
                                                                   o
            TABLE 3.1.   ACTIVITY  MATRIX  FOR  PRESAMPLING OPERATIONS
Apparatus
Sampling train
  probe and
  nozzle
Impingers,
  filter
  holders, and
  glass con-
  nectors
Pump
Dry gas meter
Acceptance limits
1.   Probe, nozzle,  and
liner free of contami-
nants; constructed  of
borosilicate glass,
quartz, or equivalent;
metal liner must be
approved by admini-
strator
                 2.
                 at
    Probe
   380 mm
leak free
(15 in.) Hg
                 3.   Probe heating
                 system prevents  mois-
                 ture condensation
Clean; free of breaks
cracks, leaks, etc.
Sampling rate of 0.02-
0.03 mVmin (0.7 to
1.1 ftVmin) up to 380
mm (15 in.) Hg at pump
inlet
Clean; readings ±2% of
of average calibration
factor
               Frequency  and method
                  of  measurements
               1.   Clean  internally
               by  brushing with tap
               water,  deionized dis-
               tilled  water, and
               acetone; air dry
               before  test
2.  Visual-ly check
before test

3.  Check heating
system initially and
when moisture cannot
be prevented during
testing (Sec 3.4.1)
               Clean  with  detergent,
               tap water,  and
               deionized distilled
               water
               Service  every  3  mo
               or upon  erratic  be-
               havior;  check
               oiler jars  every 10
               tests
               Calibrate  according
               to Sec  3.4.2;  check
               for excess oil
                       Action  if
                       requirements
                       are not met
                       1.   Repeat
                       cleaning  and
                       assembly  pro-
                       cedures
2.   Replace
                                                3.   Repair or
                                                replace
                                                        O
                       Repair or
                       discard
                       Repair or re-
                       turn to manu-
                       facturer
                       As above
(continued)
                                                                  O

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                                                       Section No.  3.10.3
                                                       Revision No.  0
                                                       Date January 4, 1982
                                                       Page 3  of 3
TABLE 3.1 (continued)
Apparatus
Acceptance Tirolts
Frequency and method
   of measurements
Action if
requirements
are not met
Reagents and
  Equipment

Filters
No irregularities,
flaws, pinhole leaks;
<0.015 mgF/cm2
Visually check before
testing; check each
lot of filters for F
content
Replace
Water
Deionized distilled
conforming to
ASTM-D1193-74, Type 3
Run blank evapora-
tions before field
use to eliminate high
solids (only required
if impinger contents
to be analyzed)
Redistill or
replace
Stopcock grease
Acetone insoluble;
heat stable
Check label  upon
receipt
Replace
Packing Equip-
  ment for
  Shipment

Probe
Rigid container lined
with polyethylene foam
Prior to each ship-
ment
Repack
Impingers, con-
  nectors, and
  assorted
  glassware
Rigid container lined
with polyethylene foam
As above
As above
Pump
Sturdy case lined with
polyethylene foam ma-
terial if not part of
meter box
As above
As above
Meter box
Meter box case and/or
additional material to
protect train compon-
ents; pack spare meter
box
As above
As above
Wash bottles
  and storage
  containers
Rigid foam-lined con-
tainer
As above
As above
                                                                            A

-------
o
o
o

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                                             Section No. 3.10.4
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 1 of 3
4.0  ON-SITE MEASUREMENTS
     The  on -site  activities  include  transporting  equipment to
the  test  site, unpacking  and assembling  the  equipment,  making
duct measurements, performing the velocity traverse, determining
molecular weights  and  stack gas moisture contents,  sampling for
particulates, and  recording the data.   Table 4.1 summarizes the
quality assurance activities for on-site activities.  Blank data
fornvs are in  Sections  3.9.12  and 3.10.12 for the convenience of
the  Handbook user.   This  section  is the  same as  Method 13B
(Section 3.9.4).

-------
                                                      Section  No. 3.10.4
                                                      Revision No.  0
                                                      Date January  4,  1982
                                                      Page 2 of 3
                                                                   o
          TABLE 4.1.   ACTIVITY MATRIX  FOR ON-SITE MEASUREMENT CHECKS
Apparatus
Sampling

Filter
Condenser
  (addition of
  reagents)
Assembling
  sampling
  train
Sampling
  (isokineti-
  cally)
Acceptance limits
Centered in holder;  no
breaks, damage, or con-
tamination during
loading
100 ml of distilled
water in first two
impingers; 200-300 g of
silica gel in fourth
impinger
1.  Specifications
in Fig 1.1
                 2.   Leak rate <4% of
                 sampling volume  or
                 0.00057 m3/min (0.02
                 ftVmin), whichever is
                 less
1.  Within ±10% of
isokinetic condition
and at a rate of less
than 1.0 ftVmin

2.  Standard checked
for minimum sampling
time and volume; sam-
pling time >2 min
point      "~
Frequency and method
   of measurements
Use tweezers or surg-
ical gloves to load
Use graduated cylinder
to add water, or weigh
each impinger and its
contents to the near-
est 0.5 g
1.  Check specifica-
tions before each
sampling run

2.  Leak check before
sampling by plugging
nozzle or inlet to
first impinger and
pulling a vacuum of
380 mm (15 in.) Hg
1.  Calculate for
each sample run
                                          2.   Make  a  quick cal-
                                          culation  before test,
                                          and  exact calculation
                                          after
Action if
requirements
are not met
Discard fil-
ter, and
reload
Reassemble
system
                                                                                   O
1.   Reassem-
ble
                                                2.  Correct
                                                the leak
1.  Repeat
the test run
                       2.   As above
                                                                                  O
(continued)

-------
                                                      Section No. 3.10.4
                                                      Revision No.  0
                                                      Date January  4,  1982
                                                      Page 3  of 3
TABLE 4.1 (continued)
Apparatus
Sample recovery
Sample
  logistics,
  data collec-
  tion, and
  packing of
  equipment
Acceptance limits
                 3.   Minimum number  of
                 points  specified  by
                 Method  1
                 4.   Leakage  rate
                 <0.00057 mVmin (0.02
                 ftVmin) or  4% of  the
                 average sampling vol-
                 ume, whichever is  less
Noncontaminated sample
1.  All data recorded
correctly
                 2.   All  equipment  exam-
                 ined for damage  and
                 labeled  for shipment
                 3.   All  sample  contain-
                 ers  and  blanks  properly
                 labeled  and  packaged
Frequency and method
   of measurements
                         3.   Check'before the
                         first  test  run  by mea-
                         suring duct and using
                         Method 1
                         4.   Leak  check  after
                         each test run or be-
                         fore equipment  re-
                         placement during test
                         at  the  maximum  vacuum
                         during  the test (man-
                         datory)
Transfer sample to
labeled polyethylene
container after each
test run; mark level
of solution in the
container
1.   After each test
and before packing
                         2.   As  above
                         3.   Visually check
                         after  each  sampling
Action if
requirements
are not met
                       3.   Repeat
                       the  procedure
                       to comply
                       with specifi-
                       cations  of
                       Method 1

                       4.   Correct
                       the  sample
                       volume or re-
                       peat the sam-
                       pling
Repeat the
sampling
1.   Complete
the data
                       2.   Repeat
                       the  sampling
                       if damage
                       occurred dur-
                       ing  the test

                       3.   Correct
                       when possible

-------
o
o
o

-------
                                             Section No.  3.10.5
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 1 of 18
5.0  POSTSAMPLING OPERATIONS
     The postsampling operations include checks on the apparatus
used in  the field during sampling to  measure  volumes,  tempera-
tures,  and  pressures,  and analyses of  the  samples  collected in
the field  and forwarded to  the base laboratory.   Table  5.1 at
the end of this section summarizes the quality assurance activi-
ties for the postsampling operations.
     The postsampling checks on the  sample  collection train are
the  same as  for Method  13B  (Section  3.9.5).  The  analytical
method is different with  exception  of some  of the sample prepa-
ration.   The  entire  analytical  procedure   is detailed  below.
5.1  Base Laboratory Analysis
     All fluoride samples should  be  checked by the analyst upon
receipt  in  the base  laboratory  for  identification  and  sample
integrity.  Any  losses  should be noted on  the  analytical  data
form (Figure  5.1).   Either  void the sample or correct  the data
using  a  technique approved by  the administrator.   If a notice-
able amount of sample has  been lost by  leakage,  the following
procedure may be used to correct the volume.
     1.   Mark the new level of the sample container.
     2.   Treat the sample  as  described in  Subsection 5.2.3 and
note the final dilution volume (vsoin)•
     3.   Add  water  up to  the initial mark  on the  container,
transfer the  water  to a graduated cylinder and  record  the ini-
tial sample volume (vsoini)  i-n milliliters.
     4.   Add water to the  new mark on the  container.  Transfer
the water  to a graduated cylinder,  and record the  final  volume
       ) in milliliters.
     5.   Correct the  volume  by  using the  following equation:

              v      = V      Vsolni
               soln     soln  Vsolnf

-------
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                                                                                                                       M
                                                                                                                       ws   in
                                                                                                                       O9
                                                                                                                       K>
                                       Figure 5.1.  Method  13A analytical  data fora.
<
        O
                                                            O
                                                                O

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                                             Section No. 3.10.5
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 3 of 18

where
     Vsoln' = samPle v°lume to  be  used in the calculations, ml;
       soln = total volume of solution in which fluoride is con-
              tained, ml;
     V  ,  . = initial  volume  added  to  the  container  in  the
field, ml;
     Vsolnf = ^na-'-  v°lume removed  from  the  container in the
base laboratory, ml.
     6.   Both  the corrected  and  uncorrected values  should be
submitted in the test report to the agency.
     If the spent silica was not weighed in the field, weigh the
silica gel  and report the weight  to  the  nearest 0.5 g on the
sample integrity and recovery form.
     In the SPADNS  colorimetric method,  the volume measurements
of- the sample and the reagents are very important to the accura-
cy of  the determination.  The  temperatures of the  samples and
standards not  only must be within 2°C  (4°F), but also must be
constant  throughout color  development.  Calibration  curves may
be prepared for different  temperatures.   The analytical balance
must be checked with Class-S standard weights before each series
of weighings, and  the  data on the weighings must be recorded on
a calibration form  (Figure 5.2).
     The  colorimetric  method is based on  the reaction between
flouride and a zirconium-dye;  more specifically,  fluoride reacts
with the  dye lake,  and dissociates a portion of  the  dye into a
colorless  complex  anion  (ZrF7) and  the dye.  As  the amount of
fluoride  increases,  the  color  either  becomes  progressively
lighter  or  changes in  hue.   The  reaction  rate between  the
fluoride and zirconium ions is accelerated by the acidity of the
reagent;  by increasing the proportion of acid, the reaction can
be practically instantaneous.

-------
Balance  name
Bfcfat
Number
Classification of standard weights
                                                   Section  No.  3.10.5
                                                   Revision No. 0
                                                   Date January 4, 1982
                                                   Page 4 of 18
                                                   <£"V?-/.
                                         o
Date
r/7//o
0.5000 g
0- S~ooi
1.0000 g
a 9?f^
10.0000 g
/O. OOO
50.0000 g
S~ ' O. OooJ
100.0000 g
/CO. 006*.
Analyst
A£6
                                                                                o
              Figure 5.2.  Analytical balance calibration form.
                                                                               o

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                                             Section No. 3.10.5
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 5 of 18

     Colorimetric methods are subject to errors from interfering
ions;  thus  it  will  be necessary  to distill the  sample before
making the fluoride determination.                           "
     Procedures  are  detailed  herein  for  preparing  reagents,
blanks,  control samples,  distillation  aliguots,  reference and
working standards, and measuring the fluoride in samples.
5.2.1   Reagents'- The  following  reagents  are  needed  for the
analyses of fluoride samples.
     1.   Calcium oxide (CaO) - ACS  reagent grade  powder or ACS
certified grade containing <_0.005% fluoride.
     2.   Phenolphthalein indicator - 0.1%  in 1:1  ethanol-water
mixture (v/v).
     3.   Sodium hydroxide (NaOH)  -  Pellets, ACS  reagent grade
or the equivalent.
     4.   Sulfuric acid (HgSO4)  -   Concentrated,   ACS  reagent
grade or the equivalent.
     5-   Filters - Whatman No'. 541 or the equivalent.
     6-   Water - Deionized  distilled to conform to ASTM speci-
fication D1193-74, Type  3.   The analyst may omit the KMn04 test
for oxidizable  organic  matter if high concentrations of organic
matter are not expected.
     7.   Silver sulfate (Ag^SO.)  -  ACS reagent  grade  or the
equivalent.
     8.   Hydrochloric acid  (HC1)  -  Concentrated,  ACS  reagent
grade or the equivalent.
     9.   Sodium fluoride (NaF) standard  -  Dissolve  0.2210 g ±
0.0005 g ACS reagent grade NaF, which has been dried for a mini-
mum  of 2  h at  110°C (230°F)  and stored  in a desiccator,  in
                *
deionized  distilled  water,  and  dilute  to  1-Jl with deionized
distilled water; this solution contains 0.1 mgF/ml.
    10.   Sodium fluoride (NaF) working standard - Pipette 100
ml of the NaF standard into a l-£ volumetric flask and dilute to
mark with deionized distilled water; this solution contains 0.01
mg F/ml.

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o
                                             Section NO. 3.10.5
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 6 of 18

    11.   SPADNS solution  -  Dissolve  0.960  ±0.010 g  of SPADNS
reagent 4,5  dihydroxy-3-(parasulfophenylazo)-2,7-naphthalenedi-
sulfonic acid  trisodium salt  (also  called sodium 2-(parasulfo-
phenylazo)-l,8-dihydroxy-3,6~naphthalenedisulfonate)   in   dis-
tilled water,  and  dilute  to  500 ml; this solution is stable for
about 1 mo  if  stored in a well-sealed bottle and protected from
direct sunlight.
    12.   Reference solution -  Add 10 ml  of SPADNS solution to
100 ml of distilled water; dilute 7 ml of concentrated HCl to 10
ml with distilled  water and add it to the diluted SPADNS solu-
tion.  Prepare  the reference  solution fresh daily and use it to
set the spectrophotometer zero point.
    13.   SPADNS mixed reagent  -  Dissolve  0.135  ±0.005  g  of
zirconyl chloride  octahydrate (ZrOCl2 •  8H20) in 25  ml of dis-
tilled water; add  350 ml of concentrated HCl; and finally dilute        ^^^
to 500 ml with distilled water to get the zirconyl acid reagent.        f   )
Then, mix equal volumes of the SPADNS solution and zirconyl acid
reagent to produce the SPADNS mixed reagent, which is stable for
at least 2 mo.
5.2.2  Blanks  - The three blanks needed for  the analysis are a
filter blank to ensure that the quality of the filter is accept-
able,  a  distillation blank to  protect against cross contamina-
tion,  and  a sample blank to analyze  with  the samples to verify
the purity of the  reagents used in sampling and analysis.
     •1.  • Filter blanks -  Determine  the  fluoride content of the
sampling  filters  upon receipt  of  each new  lot  of and at least
once  for  each test  series.    Initially,  select  three filters
randomly from each lot.
                *
           a.    Add each filter  to 500  ml of  distilled water.
          b.    Treat  the  filters  exactly like a  sample  (Subsec-
tion 5.2.3).
           c.    Use a  200-ml   aliquot  for   distillation.   The
fluoride  concentration of  the filter blank must  be <0.015 mg
F/cm2;  if not,  reject this  batch and  obtain a  new supply of
filters.

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                                             Section No. 3.iu.s
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 7 of 18

     2.   Distillation blank  -  Check the condition  of the acid
in the  distillation  flask (Subsection 5.2.5) for cross-contami-
nation  after every  10th sample by  adding  220 ml  of distilled
water  to  the still pot and then proceed  with  the analysis.  If
detectable  amounts  of fluoride (>0.1 jjg  F/ml)  are  found in the
blank, replace the acid in the distillation flask.
     3.   Sample blank -  Prepare the sample blanks in the field
at the same  time  and with  the same reagents used  for sample
recovery.
          a.   Add an unused  filter  from the same batch used in
sampling  to a volume  of distilled  water equal  to  the average
amount used to recover the samples.
          b.   Treat the  sample blank in the same manner as the
aamples are  treated  (Section  5.2.3).  Analyze the sample blanks
 ith the samples.
5.2.3  Sample Preparation  - Use the  following  procedure to pre-
pare samples for distillation.  Distillation is not required if
it can be shown to  the  satisfaction of  the Administrator that
fluoride results are unaffected by the alternate analytical pro-
cedure  (e.g.,  ash  and fusion of particulate matter with subse-
quent  ion  selective electrode  analysis,  or  direct  electrode
analysis of gases trapped in impingers).
     1.   Filter the contents of the sample container (including
the  sample  filter)  through  a Whatman  No.  541  filter  or the
equivalent into a 1500-ml beaker;  if the filtrate volume is >_900
ml, add NaOH  to  make the filtrate basic to phenolphthalein, and
then evaporate to <900 ml.
     2.   Place  the  Whatman No. 541 filter containing  the in-
oolubles (including the sample filter) in a nickle crucible, add
a few milliliters of water;  and macerate the filter with a glass
rod.
     3.   Add 100 mg or sufficient quantity of CaO to the nickel
crucible  to make  the  slurry basic;  mix thoroughly; and  add a
couple drops of phenolphthalein indicator, which turns pink in a
basic medium.  Note;   If the slurry does not remain basic (pink)

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                                             Section No. 3.10.5
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 8 of 18             ^~^

during the  evaporation of the water, fluoride  will  be lost; if
the slurry becomes  colorless,  it is acidic so add C'aO until the
pink returns.
     4.   Place  the crucible  in a  hood area  either  under in-
frared lamps  or on a  hot plate at low heat (approximately 50-
60°C)  (122-140°F),   and  evaporate  the  water  completely;  then
place  the  crucible  on  a  hot plate under a  hood and slowly in-
crease the temperature  for  several  hours or until the filter is
charred.
     5.   Place the crucible in a cold muffle furnace and gradu-
ally  (to prevent  smoking)  increase the  temperature  to  600°C
(1112°F); maintain  the temperature  until  the crucible contents
are  reduced  to  an  ash  containing no  organic materials;  and
remove the crucible from the furnace to cool.
     6.   Add  approximately  4 g of crushed  NaOH pellets to the       ^^^
crucible, and  mix;  return the crucible to the furnace, arid fuse       f  )
the  sample  for  10  min at 600°C (1112°F);  and  then remove the
sample  from  the furnace,  and  cool it  to  ambient, temperature.
     7.   Use several rinsings of warm distilled water to trans-
fer  the  contents of the  crucible   to the  beaker containing the
filtrate (step 1) and finally, rinse the crucible with two 20-ml
portions of 25%  (v/v) H2S04, and carefully add the rinses to the
beaker.
     8.   Mix1 well,  and transfer the  beaker contents  to  a l-£
volumetric  flask.   Record  the volume  as  Vt on the  data  form
(Figure  5.1).   Dilute  to volume with distilled water,  and mix
thoroughly; and allow any undissolved solids to settle.
5.2.4  Acid-water Ratio - The acid-water ratio in the distilla-
tion flask should be  adjusted by following this procedure.  Use
a protective shield when carrying out the procedure.
     1.   Place  400 ml  of distilled water in the 1-A distilling
flask,  and add  200 ml of  concentrated H2SO4.   Slowly add the
H2S04, while constantly swirling the flask.
     2.  .Add  soft  glass  beads and  several  small  pieces of
broken glass tubing, and  assemble the apparatus.
o

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                                             Section No. 3.10.5
                                             Revision No. 0
                                             Date January 4, 1902
                                             Page 9 of 18

     3.   Heat the flask until it reaches a temperature of 175°C
 (347°F),  and  discard the  distillate,  and  hold the  flask for
 fluoride separation by distillation.
 5.2.5   Fluoride Separation (Distillation)  -  Fluoride  can  bo
 separated from other  constituents  in the aqueous sample by dis-
 tilling  fluosilicic   (or hydrofluoric)  acid from a  solution of
 the sample in an acid with a higher boiling point.  Samples with
 low concentrations of fluoride (e.g.,  samples from an outlet of
 a scrubber) should be distilled first to eliminate contamination
 by carryover of  fluoride  from the previous sample.  If fluoride
 distillation in the milligram range is to be followed by distil-
 lation  in  the fractional  milligram range,  add  200  ml  of de-
 ionized distilled  water and  redistill  similar to the  acid ad-
 justment procedure,  Subsection 5.2.4,  to  remove residual fluo-
 ride from the distillation system.
     1.   Cool the contents  of  the  distillation  flask (acid-
 water adjusted) to <80°C (176°F).
     2.   Pipette  an  aliquot  of sample  containing <10.0  mg  F
 into the distillation'flask, and add distilled water to make 220
 ml.  The  aliquot size  (At)  should be entered on the data form
 (Figure 5.1).  Note;   For an estimate of  the  aliquot size that
 contains £10 mg F,  see Subsection 5.2.7.
     3.   Add  5  mg silver  sulfate (Ag2S04)/mg  chloride  to the
 distillation flask; if  the  sample contains chloride,  use proce-
 dures  described  in Subsection  5.2.8  to determine  the chloride
 concentration.
     4.   Place a 250-ml volumetric flask at the condenser exit;
 heat the distillation  flask as rapidly as possible with a burn-
               •
 er, while moving the flame up and down the sides of the flask to
prevent bumping;  conduct the distillation as rapidly as possible
 (175°C (347°F) will  cause  H2SO.i to
 distill over.  Note;   The H2S04 in the  distillation flask can bo

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                                             Section No. 3.10.5
                                             Revision No.  0
                                             Date January 4, 1982
                                             Page 10 of 18

reused until  carryover  of interferent  or until poor fluoride
recovery  is  shown  by  the distillation  blanks  or  the control
samples.
     5.   Before  distilling the  field samples  and  after every
tenth  distillation  of any  sample,  distill a control  sample to
check  the analytical  procedures  and  interferences  (Subsection
5.2.6).
5.2.6  Control Samples  -  A  control  sample  should  be used to
verify  the  calibration  curve and the   distillation  recovery
before and  during the  analysis of the  field samples.  Use the
following procedures.   Data  should be recorded on  the control
sample analytical data form (Figure 5.3).
     1.   125 mg F/£ NaF control sample stock solution   -   Add
0.276  g   of  reagent  grade anhydrous  NaF  to a 1-2 volumetric
fl'ask; add enough distilled water to dissolve? and dilute to 1-Ji
with distilled water.
     2.   2.5 mq F/£ NaF distillation solution  - Pipette  20 ml
of  the 125  mg  F/A  stock  solution  into  a I-i volumetric flask,
and  dilute  to the  mark with distilled water to get the 2.5 mg
F/je. NaF  distillation solution.  Distill 200 ml  of this solution
according to Subsection  5.2.5.
     3.   Pipette  4.0 ml  of  the  control  sample stock solution
into a 250-ml  volumetric flask and dilute to the mark with  dis-
tilled water.    Analyze this  solution colorimetrically  in the
came  manner as  the samples  are  analyzed (Subsection 5.2.10).
5.2.7  Distillation Alio^iot - The sample volume  for  distillation
ohould contain <10 mg F.   Use  the  following procedure to esti-
nate the  aliquot  size.
     1.   Pipette a 1.0-ml aliquot  of  sample  into a  polyethylene
beaker.
     2.   Add  50 ml of distille'd water.
     3.   Analyze by the procedure  described  in  5.2.10.

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                                                     Section No.  3.10.5
                                                     Revision No. 0
                                                     Date  January 4,  1982
                                                     Page  11 of 18
Plant     flew P.   Fer-ti \\7-tf
                                               Date of analysis
Analyst    (j) .
                           I I
Ambient temperature
Date of calibration curve   5j/3/?0     Temp, of calibration curve  3 /
                                       Concentration of control sample
                                       Distilled
                                                          Undi stilled
                                                            0.475

                                                             3D. I
Control sample temperature                
-------
                                             Section No. 3.10.5
                                             Revision No. 0            /"""N
                                             Date January 4, 1982      {}
                                             Page 12 of 18
     4.   Determine the (jg  of  F in the nondistilled sample from
the  calibration  curve, and determine  the  maximum size  of the
aliquot for distillation by substituting the amount of F (ng) in
the nondistilled sample in the following equation:

aliquot for distillation «1, =

        = Mg F1d4teLined     Vhen aj1'0 ml nondistilled aliquot
           3                  is used.
If the  amount of F  in the nondistilled. sample is >70  pg, de-
crease  the aliquot  taken  for this  estimation and  change the
aliquot value  input  into the  above  equation.   The aliquot size
is only  an approximation since  the  interferring  ions  have not
been removed  by  distillation.   If the  estimate  is >220 ml, use
220 ml; if it is <220 ml, add distilled water to make the total
volume  added   to the  distillation flask  220  ml;  if required,
dilute the sample so that a minimum 1-ml sample aliquot is added
to the distillation flask.
5.2.8  Determination  of Chloride  - A  chloride  determination is
necessary because of  major  interferences with Method 13A when a
relatively high concentration of chloride ions (Cl~) are present
in the collected sample.   Chloride concentration depends on the
plant's material balance.
     The mercuric nitrate procedure is  introduced here for esti-
mating  how much Ag2SO4  is required  for  removal of  chloride
interference.   This  procedure  is  easy to perform  and  has good
precision  and  accuracy.    Reagents  needed  for  this  procedure
follow:
     !•   Standard sodium chloride solution (NaCl), 0.141 N
Dicsolve 8.241 g NaCl (dried at 140°C  (285°F) for 1-h) in chlo-
ride-free water,  and dilute to l-£; contains 5 mg Cl/ml.
     2.   Nitric acid  {HNO.7), 0.1 N  -  Dilute  5  ml  of concen-
trated HNO3 to 800 ml with distilled water.

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                                             Section Ho. 3.10.5
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 13 of 18

     3.   Mixed indicator reagent - Dissolve 5 g of diphenylcar-
bazone powder  and  0.5  g of bromphenol blue powder  in  750 ml of
95% ethyl or  isopropyl alcohol,  and dilute to 1 $, with the same
alcohol.
     4.   Standard mercuric nitrate (Hg(NOa)g) titrant, 0.141 N -
Dissolve 25 g  of  Hg(NO3)2'H2O in 900 ml of distilled water con-
taining 5 ml of concentrated HN03 (nitric acid).  Dilute to 1 £.
The chloride equivalent of the titrant is 5.00 mg/ml.
     The sample analysis for chloride  determination is as fol-
lows:
     1.   Pipette 25 ml of a sample into a 150-ml beaker.
     2.   Add  approximately  0.5  ml of  indicator,  and mix well;
the color should be purple.
     3.   Add  0.1N HNO3  drop-by-drop  until the color just turns
ye.llow.
     4.   Titrate with 0.141N Hg(NO3)2 to  the first appearance
of dark purple and record the number of milliliters used.
     5.   Check the blank by titrating 100 ml of distilled water
containing 10 mg NaHC03 .
     6.   Calculate  the  concentration  of  chloride  with  the
following equation.
              Of Cl .  (A -    ^,5,450
where
     A = titrant used for sample, ml,
     B = titrant used for blank, ml, and
     N = normality of Hg (N03)2/ meg/ml.
     Standardization of Hg (N03)2 for Chloride -
     1.   Titrate  15 ml  of the standard NaCl  with Hg  (N03)2
reagent,  using the  method  as   previously  described.  Make  at
least  three  replicates  and obtain  the  average normality  of  Hg
(N03)2.

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                                              Section No.  3.10.5
                                              Revision No.  0
                                              Date January 4,  1982
                                              Page 14 of 18

      2.   Calculate the normality of Hg (N03)2«
          ml NaCl x N NaCl = ml Hg(NO3)2 x N Hg (N03>2;
therefore,
          N HofNO ^  - ml NaCL x N NaCl
          N Hg(N03)2 	mi Hg(NO3)2
      3.   Calculate and  add the required  amount of silver sul-
 fate for each sample:
          __ .„ cn  _ mg/E Cl" x ml aliquot (distilled) x 5
          mg Ag2S04 -    	1000 mi	

 5.2.9  Calibration Standards  - Use the  sodium  fluoride working
 standard in Subsection  5.2.1  (0.01 mg/ml)  in the following pro-
 cedure.  These  standards  cover the range of 0.2  -  1.4 pg F/mJi.
      1.   Pipette 2.0,  4.0,  6.0,  8.0,  10.0,  12.0,   and  14.0 ml
 volumes of 0.01 mg  F/ml NaF solution into seven separate 100-ml    C j
 volumetric flasks, and  dilute  to the mark with distilled water.
      2.   Pipette 50 ml of each of the each solutions into sepa-
 rate  100-ml  polyethylene  beakers,  add 10 ml  of  SPAPNp  mixed
 reagent to each, and mix well.
      3.   Prepare  the  blank  standard by  pipetting  10  ml  of
 SPADNS mixed  reagent to 50 ml of  dictilled water.   These stan-
 dards  will  contain  0,  10,  20,  30,  40,  50, 60,  and 70  pg of
 fluoride.
      4.   After  mixing-,  place  the  calibration standards  and
 reference  solution  Subsection 5.2.1  in a  constant temperature
 bath for  30  minutes before  reading the absorbance  within ±3°C
 (5.4°F) of the  spectrophotometer.   Note;   Adjust all samples to
 this same  temperature before  analysis.  Since  a 3°C difference
 between samples and  standards  will produce an error of approxi-
 mately 0.005 mg F/£, take care to see that samples and standards
 are  at  nearly identical temperatures  when absorbances are mea-    ^_^^
 sured.                                                              f  )
 5.2.10  Determination of Fluoride Concentration - In Method 13A,
 use  the  following  steps  to  determine the amount  of fluoride.

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                                             Section No. 3.10.5
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 15 of 18

     1.   Dilute the  distillate  to  the mark in the 250-ml volu-
metric  flask with  distilled  water,  and mix  thoroughly.  Enter
this volume  (V^) on the analytical data form (Figure 5.1).
     2.   Pipette a suitable aliquot (maximum of 50 ml) from the
distillate  (containing  10  to  40  pg F) (for the control samples,
a  10  ml  aliquot  is required);  dilute to 50 ml  with distilled
water;  add  10 ml of  SPADNS mixed reagent;  and mix thoroughly.
Record the aliquot A^ on the data form.
     3.   Place the sample in a bath that is  constant at ±3°C
(5.4°F) of  ambient  temperature  and which contains the standard
solutions for 30 min before reading absorbance with the spectro-
photometer.
     4.   Warm up the spectrophotcmeter  for  a  suitable time (5
to 10  min)  depending on  the  instrument;  set  the photometer to
zero  absorbance  with the  reference   solution  at  570  nm;  and
immediately  obtain  the  absorbance readings  of  the standards,
control sample, and field samples.
     5.   Prepare a calibration curve by plotting the micrograms
(M9)  F/50 m£  versus  absorbance  on  linear graph  paper,  as de-
scribed in  Section  3.10.2.  Note:  Prepare a new standard curve
whenever  a  fresh batch  of any reagent is made up or when a dif-
ferent  standard  temperature  is  desired.   Also,  run  an undis-
tilled  control  sample with each set of  samples;  if it differs
from  the  calibration curve  by   >±2%,  prepare  a new standard
curve.
     6.   Determine the  pg fluoride from  the calibration curve
and record  on the  data form  (Figure  5.1).  The  values  of the
control samples should  be  20  jjg.  For the undistilled sample, a
value between  3*9.6  and  20.4 pg is acceptable; for the distilled
sample,  a  value  between  18.0  and  22.0  pg  is  the acceptable
range.  If both values for the control samples fall within their
limits,  the  field  sample  results  should also  be  acceptable.
However,  if the  undistilled  sample  is acceptable and the dis-
tilled  is not,  replace the contents  of the  distillation flask
and redistill  all  samples.   If  the distilled  is  acceptable and

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                                             Section No. 3.10.5
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 16 of 18            /^\

the undistilled  sample is not, prepare  fresh calibration stan-
dards  and carefully  check the  temperature  equilibrium.   When
both samples are  unacceptable, prepare  a new calibration curve.
If this  does  not correct  the  problem,   start  over  with all  new
solutions and check with an analyst familiar with the procedure.
     7.   Repeat  the  procedure using a  smaller  size aliquot of
distillate if  the fluoride concentration  of the sample  is  not
within the range of the calibration curve.
     8.   Calculate the total  weight  as  milligrams  and the con-
centration of fluoride using the equations in Section 3.10.6 and
record on the data form (Figure 5.1).
     The  value of  F^  obtained  using Equation  6.4  of Section
3.10.6  for  the  distilled  control sample  should be  2.50  mg F;
acceptable values are  between 2.25  and 2.75 mg F.   The final
emission  concentration in mg/dscm (Ib/dscf)  should be reported       -^
in the  test report  to the agency both corrected and uncorrected      (   )
for the sample blank.
                                                                      o

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                                                      Section No.  3.10.5
                                                      Revision No.  0
                                                      Date January 4, 1982
                                                      Page 17 of 18
            TABLE 5.1.   ACTIVITY  MATRIX FOR POSTSAMPLING OPERATIONS
Apparatus
Sampling
Apparatus

Dry gas meter
Meter thermome-
  ters
Barometer
Stack tempera-
  ture sensors
Base Laboratory
Analysis

Reagents
Acceptance limits
±5% of calibration
factor
±6°C (10.8°F) ambient
temperature
±5 mm (0.2 in.) at
ambient pressure
±1.5% of the reference
thermometer or thermo-
couple
Prepare according to
Subsec 5.2
Frequency and method
   of measurements
Make three runs at a
single intermediate
orifice setting at
highest volume of
test (Sec 3.10.2)
Compare with ASTM
mercury-in-glass
thermometer after
each test
Compare with mercury-
in-glass barometer
after each test
Compare with ref-
erence temperature
after each run
Prepare a calibration
curve for each new
SPADNS reagent mix
Action if
requirements
are not met
Recalibrate;
use factor
that gives
lower gas
volume
Recalibrate;
use higher
temperature
for calcula-
tions
Recalibrate;
use lower
barometric
value for
calculations
Recalibrate;
calculate
with and
without tem-
perature cor-
rections
Prepare new
solutions and
calibration
curves
(continued)

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                                                     Section  No. 3.10.5
                                                     Rcvicion No. 0
                                                     Date January 4,  1982
                                                     Page 18  of 18
                                                                   o
TABLE 5.1 (continued)
Apparatus
Control  sample
Acceptance limits
±2% when run with
fluoride standards and
±10% when distilled
and run with field
samples
Frequency and method
   of measurements
Prepare new controls
before and during
analysis of field
samples
Action if
requirements
are not met
Prepare new
solution and
calibration
curve,  and/or
change  dis-
tillate
solution
                                                                                    O
                                                                                    o

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                                             section No.  3.10.6
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 1 of 7
6.0  CALCULATIONS
     Calculation errors  due  to procedural  or  mathematical  mis-
takes can be a large part of total system error.   Thus,  each set
of calculations should be repeated or spotchecked,  preferably by
a  team  member other  than the  one  that performed the  original
calculations.  If  a difference greater than a typical  roundoff
error is  detected,  the calculations should be checked  step-by-
step until the source of error is found and corrected.
     A computer program  is advantageous  in reducing calculation
errors.   If  a  standardized computer program is used,  the origi-
nal  data  entry should  be checked  and if differences   are  ob-
served,  a new computer run should be made.
     Table 6.1 at the end of this section summarizes the quality
assurance  activities  for calculations.   Retain  at  least  one
significant  digit  beyond that  of the acquired  data.   Roundoff
after the final calculations  for each run or sample to  two  sig-
nificant digits, in accordance with ASTM 380-76.   All  calcula-
tions should be recorded on  a calculation form such as  the  ones
in Figures 6.1A and 6.IB.
6.1  Nomenclature
     Terms used  in Equations 6-1 through 6-7 are  defined  here
for use in the sections that follow.
     A,      - Aliquot of distillate taken for color development,
      a        ml
     A       = Area of nozzle, cross-sectional, m2 (ft2)
               *
     Afc      = Aliquot of total sample added to still,  ml
     B       = Water vapor in the gas stream,  proportion by
               volume
     C       = Concentration of fluoride in stack gas corrected
      s        to standard conditions of 20°C,  760 mm Hg (68?F,
               29.92 in. Hg) on dry basis, mg/m3  (lb/ft5)
     Ft      = Total weight of fluoride in sample, mg (Ib)

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                                             Section No. 3.10.6
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 2 of 7
                                                                      o
  = £ •  2
Vm(std) B 17'64 V mY
                 SAMPLE VOLUME. (ENGLISH UNITS)
                                       ,  pbar = a
                                           ' 2
                ft8 ,  Tm = $ 5 £ . o °

                 = I . £ 2 in. H20

                    PKa + (AH/13.6)
                            - —
                                                    Equation 6-1
                  FLUORIDE CONTENT IN SAMPLE
 t = L Q. Q. (L
                                .  /) mi, vd =
                       F =
                 V  V
F.  = 2.205 x 10"9 ^-rS (Mg F) = 5 .
 r                At Ad
                                                      mi
                                            1Q~5 Ib
                                                    Equation 6-4
                                                                      o
            CONCENTRATION OF FLUORIDE
V
m(std)
   Ftb = - '
    F  — F

     m(std)
                3. 1
              = /  . a
                ~   ~
                       , Ft = 5 .


                       0"6 lb
                          io"7 Ib/dscf
                                              UNITS)
                                         10"6 Ib
                                                    Equation 6-5
    All other equations same as Methods 2 and 5.
   Figure 6.1A.  Fluoride calculation form  (English units).
                                                                      O

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                                              Section No. 3.10.6
                                              Revision No. 0
                                              Date January 4, 1982
                                              Page 3 of 7
Vm = L . 3 2 I

Y = fl • i 3 &
                  SAMPLE VOLUME (METRIC UNITS)


                   Tm = 2 L £•  °K'

                  = s2 fe-  mm H20
Vm(std) = °-3858 vm Y
                      Pbar+

                                                   mm Hg
                                                     Equation 6-1
vt ;= L Q. Q. & -

Ad = / fi . ^ ml

          V. V .
F  = 10
        -

       "
                   FLUORIDE CONTENT IN SAMPLE

                   , At = 2 a D  - Qni, vd =

                    (jg F = I % . 1 jjg


                    F) = «2 • V ^ 5 mg
                                                     Equation 6-4
            CONCENTRATION OF FLUORIDE  (METRIC UNITS)
 m(std)
            - £ 2
                         Ft =
C  =
     F. -

      m(std)
                  - 2. 3 6 mg/dscm
                                                     Equation 6-5
     All other equations same as Methods 2 and 5.
    Figure 6.IB.  Fluoride calculation form  (metric units).

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 m
                                         Section No. 3.10.6
                                         Revision No. 0
                                         Date January 4, 1982         —^
                                         Page 4 of 7                 (   )
F^,      = Total weight of fluoride in sample blank, mg (Ib)
I       = Percent of isokinetic sampling, %
M       = Molecular weight of water, 18.0 g/g-mole
          (18.0 Ib/lb-mole)
Pt.)ar    = Barometric pressure at sampling site, mm (in.) Hg
P       = Absolute stack gas pressure at sampling site, mm
 5        (in.) Hg
Pgtd    = Standard absolute pressure, 760 mm (29.92 in.) Hg
R       = Ideal gas constant, 0.066236 mm Hg-m3/K-g-mole
          (21.83 in. Hg-ft3/°R-lb-mole)
T       = Absolute average dry gas meter temperature,
 m        K (°R)
T_      = Absolute average stack gas temperature, K (°R)
 a                                                                      	
Tstd    = Slfcanc*ard absolute temperature, 293K  (528°R)                 f  j
V^      = Total volume of distillate, ml
V.      = Total volume of liquid collected in  impingers and
          silica gel, ml.  (Volume of water in silica gel =
          grams of silica gel weight increase  x i ml/g;
          volume of liquid collected in impinger = final
          volume - initial volume)
V       = Volume of gas sample measured by dry gas
          meter, dcm (dcf)
V  . ... = Volume of gas sample measured by dry gas meter
   ^    ;   corrected to standard conditions, dscm  (dscf)
V       = stack gas velocity calculated by Method 2  (Equa-
          tion 2-7) using data from Method 13, m/s (ft/s)
V       = Total volume of sample, ml
        = Vo^-ume °£ water vapor in gas sample corrected to
          standard conditions, scm (scf)
Y       = Dry gas meter calibration factor
AH      = Average pressure differential across the orifice
                                                             o
                   U A. Vv^k 1«>* A ^^b V-h^ V*>*^ V »-* k^* ^»AA^ 1^ ** ^ «to ^ t^ ^
meter, mm (in.) H20
                                                         v

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                                             Section No. 3.10.6
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 5 of 7

    p..      = Density of water,  1 g/ml (0.00220 Ib/ml)
     NV
    6       = Total sampling time,  min
    pg F    = Weight of fluoride/50 ml taken from the calibra-
              tion curve, |jg
    13.6  .  = Specific gravity of mercury
    60      = s/min
    100     = Factor for converting to percent/ %
6.2  Dry Gas Volume, Corrected to Standard Conditions
     Correct  the  sample -volume  measured by  the dry  gas meter
(Vm)  to  standard  conditions  (20°C  and  760 mm  Hg or  68°F  and
29.92 in. Hg) by using Equation 6-1.  The absolute dry gas meter
temperature  (T  )  and orific
by averaging the field data.
temperature  (T  )  and orifice pressure drop  (poor)  are obtained
          v       -VYI§td       * (AH/13.6)
          Vm(std) - VmY  Tm
                            Pbar + (AH/13.6)
                  = Kl VmY       T -       Equation 6-1.
                                  m
where
     K, = 0.3858 K/mm Hg for metric units, and
        = 17.64 °R/in. Hg for English units.
Note:  If the leak rate observed during any mandatory leak check
exceeds the acceptable rate, the tester shall either correct the
value of V   in  Equation 6-1 (Section 6.3, Method 3), or invali-
date the test runs.
                *
6.3  Volume of Water Vapor
                         Pw   R
          Vw(std) = Vic       -P     = K Vic        Equation 6-2
where
      K = 0.00133 m3/ml for metric units, and

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                                              Section No.  3.10.6
                                              Revision No.  0
                                              Date January 4,  1982
                                              Page 6  of 7
       K = 0.0472  ft3 /ml for English units.
 6.4  Moisture Content of Stack Gas
                Bws = V -    v      '              Equation 6-3
                 WB   vm(std)    vw(std)
 Note;   If  liquid droplets  are in  the  gas  stream,  assume  the
 stream to  be  saturated;  use  a psychrometric  chart to  obtain
 estimate  of the moisture percentage.
 6.5  Fluoride Content in Sample (Concentration)
              V  V, pg F
      F. = K   \ ° -                             Equation 6-4
       ^        At Ad
 where
             <*
      K =  10"  mg/pg for metric units,  and
      K =  2.205 x 10   lb/|jg for English  units.
 6/6  Concentration of Fluoride in Stack  Gas
     C  = K ..                                        Equation 6-5
      s     vm(std)
      K = 1.00 ms/m3 for metric units,  and
      K = 35.31 ft3/m3 for English units.
 6.7  Isokinetic Variation ( I )
      The isokinetic variation  ( I )  can be calculated from either
 raw data  or intermediate values using the  following equations.
 6.7.1  Calculation of I from Raw Data
       _ 100 x TS  [K Vic + (Y Vm/Tm) (Pbar + AH/13.6 )]
     1 ~               609v P A
                           s s n
                                                     Equation 6-6
where
      K = 0.003454 mm Hg-m3ml-K for metric units, and
        = 0.002669 in. Hg-ft3/ml-°R for English units.
6.7.2  Calculations of I from Intermediate Values
              x Ts vm(std)
o

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                                                   Section No.  3.10.6
                                                   Revision No.  0
                                                   Date January 4, 1982
                                                   Page 7 of  7
        = K
          T  V
          •"•S  m(std)
      VsAn e  ^-Bw
where
 6.7
K = 4.320 for  metric  units, and

  = 0.09450  for English units.

Acceptable Results
       If  90%  <.  I  £  110%,  the results  are  acceptable.   If the
 results  are low  in comparison to the  standards and if  I  is be-

 yond the acceptable  range,  the  administrator may  opt  to  accept
 the  results;  if  not,  reject the  results and repeat  the test.
Apparatus
Analysis data
  form
Calculations
Isokinetic
  variation
                 TABLE 6.1.  ACTIVITY MATRIX FOR CALCULATIONS
         Acceptance  limits
         All data  and calcula-
         tions given
         Difference between
         check and original
         calculations within
         roundoff error; one
         decimal figure re-
         tained beyond that of
         acquired data
         90% <  I  <  110%; see
         Eqs 6.6  and 6.7 for
         calculation of I
Frequency and method
   of measurements
Visual  check
Repeat  all calcula-
tions starting with
raw data for hand
calculations; check
all raw data input
for computer cal-
culations and hand
calculate one sample
per test
Calculate I for
each traverse point
Action if
requirements
are mot met
Complete the
missing data
values
Indicate
errors  on
analysis data
form
Repeat test;
adjust flow
rates to
maintain  I
within ±10%
variation
                                                                 n

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                                             Section No. 3.10.7
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 1 of 2
7.0 MAINTENANCE
     Normal  use of  emission testing  equipment subjects  it to
corrosive  gases,  temperature extremes, vibrations,  and shocks.
Keeping the  equipment in good  operating  order over an extended
time  requires  routine maintenance  and knowledge  of  the equip-
ment.  Maintenance  of the entire sampling  train should be per-
formed either  quarterly or  after 1000 ft3  of operation, which-
ever  occurs  sooner.   Maintenance  activities  are  summarized in
Table 7.1.   The following routine  checks  are recommended,  but
not required,  to  increase  reliabilty.   This section is the same
no for Method 13B (Section 3.9.7).

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                                                      Section No.  3.10.7
                                                      Revision No.  0
                                                      Date January 4, 1982
                                                      Page 2  of 2
                                                                  o
          TABLE 7.1.   ACTIVITY  MATRIX  FOR EQUIPMENT MAINTENANCE CHECKS
Apparatus
Fiber vane pump
Diaphragm pump
Dry gas meter
Inclined manom-
  eter
Other sampling
  train com-
  ponents
Nozzle
Acceptance limits
Leak free; required
flow; no erratic be-
havior
Leak-free valves func-
tioning properly;  re-
quired flow
No excess oil, corro-
sion, or erratic dial
rotation
No discoloration of or
visible matter in the
fluid
No damage or leaks; no
erratic behavior
No dents, corrosion,
or'other damage
Frequency and method
   of measurements
Periodic check of oil
and oiler jar; remove
head yearly and
change fiber vanes
Clean valves during
yearly disassembly
Check every 3 mo for
excess oil or corro-
sion; check valves
and diaphragm if
dial runs erratically
or if meter will not
calibrate
Check periodically;
change fluid during
yearly disassembly
Visually check every
3 mo; disassemble and
clean or replace
yearly
Visually check be-
fore and after each
test run
Action if
requirements
are not met
Replace as
needed
Replace when
leaking or
when running
erratically
Replace parts
as needed, err
replace meter
Replace parts
as needed
If failure
noted, re-
place meter
box, sample
box, or um-
bilical cord
 Replace noz-
 zle or clean,
 sharpen, and
 recalibrate
                                                                                   O
                                                                                   o

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                                                    Section No.  3.10.8
                                                    Revision  No. 0
                                                    Date January 4,  1982
                                                    Page 1 of 1
 8.0  AUDITING PROCEDURES

       An  audit  is  an  independent  assessment  of  data  quality.

 Independence  is achieved by using apparatus and standards that

 are different  from  those used by  the regular,  field crew.   Rou-

 tine quality  assurance  checks by a  field team  are necessary  for

 obtaining  good  quality data,  but  they  are  not  part of  the  au-

 diting  procedure.   Table 8.1  summarizes  the   quality  assurance

 activities  for the  auditing.   This section is the same  as Method

 13B (Section 3.9.8).

             TABLE 8.1.  ACTIVITY MATRIX FOR AUDITING PROCEDURES
Audit
Performance
Audit

Analytical
  phase  of
  Method 13 A
  using  aqueous
  sodium fluo-
  ride
Data processing
  errors
Systems audit
Acceptance  limits
Measured  concentrations
of audit  sample within
acceptable limits of
true value, Section
3.9.8
Difference between
original and audit
calculations within
roundoff error
Operation technique as
described in Section
3.10.8
Frequency and method
   of measurement
Once during every
enforcement source
test; measure audit
samples and compare
their values with
known concentrations
Once during every
enforcement source
test, perform inde-
pendent calculations
starting with data
recorded on field
and laboratory forms
Once during every
enforcement test,
until  experience
gained and then
every fourth test,
observe techniques;
use audit checklist
(Fig 8.2, Section
3.9.8)
Action if
requirements
are not met
Review
operating
technique
Check and
correct all
data; recal1
culate if
necessary
Explain  to
team devia-
tions from
recommended
techniques;
note on
Fig 8.2

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                                             Section No. 3.10.9
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 1 of 1
9.0  RECOMMENDED STANDARDS FOR ESTABLISHING TRACEABILITY
     To  acquire  data  of good  quality,  two  considerations  are
essential:
     1.   The measurement process must  be in a state of statis-
tical control at the time of the measurement, and
     2.   The systematic errors,  when  combined  with the random
variations  (errors  of measurement),  must result  in acceptable
uncertainty.
Other  quality  assurance  activities  include  quality  control
checks  and independent  audits  of the  total  measurement system
(Section 3.10.8); documentation of data by using quality control
charts  (as  appropriate);  use  of  materials, instruments,  and
  *
procedures that can be traced to appropriate standards of refer-
ence;  and use of control standards  and working  standards  for
routine  data  collection and  equipment  calibration.   Working
standards should be traceable to primary standards:
     1.   Dry gas meter calibrated against a wet test meter that
has  been verified by  liquid  displacement (Section 3.9.2)  or by
a spirometer.
     2.   Field  samples,  analyzed by  comparisons  with standard
solutions  (aqueous  NaF)  that have  been validated with indepen-
dent control samples.

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   ilO.O    REFERENCE  METHOD3
                                                                                 Section  No.  3.10.10
                                                                                 Revision  No.   a
                                                                                 Date  January   4,   1982
                                                                                 Page  1  of 5
    40 CFR Part 60 is amended by revising
  Methods ISA and 13B of Appendix A to
  read as follows:

  Appendix A—Reference Test Method* •
  •     *    »     *     •

  Method 13A. Determination of Total Fluoride
  Emissions From Stationary Sources; SPADNS
  Zirconium Lake Method
  1. Applicability and Principle
   1J  Applicability.  This method applies to
  the determination of fluoride (F] emissions
  from sources as specified in the regulations. It
  does not measure fluorocarbons. such as
  freons.
   1.2  Principle.  Gaseous and paniculate F"
  •rs withdrawn i*okin«tic»liy from the source
  end collected in water and on a filter. The
  total F is then determined by the SPADNS.
  Zirconium Lake  colorimetric method.
  Z Range and Sensitivity
   The range of this method is 0 to 1.4 fig F/
  ml Sensitivity has not been determined.
3. Interferences
  Large quantities of chloride will interfere
  th life analysis, but this interference can bt-
   ivented by adding silver suifate into the
 IsHllation flask (see Section 7.3.4). If
Chloride ion is present, it may be easier to u»»
the Specific Ion Electrode Method (Method
13B). Grease on sample-exposed surfaces
may cause low F results due to adsorption.

* Precisian. Accuracy, and Stability
  4.1  Precision. The following estimates
ar« based on a collaborative test done at a
primary aluminum smelter. In the test, six
laboratories each sampled the stack.
simultaneously using two sampling trains for
a total of 12 samples per sampling run.
Fluoride concentrations encountered during
the test ranged from 0.1 to 1.4 mg F/m1.. The
within-laboratory and between-laboratory
standard deviations, which include sampling
and analysis errors, were 0.044 mg F/m3 with
60 degrees of freedom and 0.064 mg F/m3
with five degrees of freedom, respectively.
  4.2  Accuracy.  The collaborative test did
not find any bias in the analytical method.
  4.3  Stability.  After the sample and
colorimetric reagent are mixed, the color
formed is stable for approximately 2 hours. A
3*C temperature difference between the
sample and standard solutions produces an
error of approximately 0.005 mg F/liter. To
avoid this error, the absorbances of the
tample and standard solutions must be-
measured at the same temperature.
5. Apparatus
  5.1  Sampling Train,  A schematic of the
sampling train is shown in Figure 13A-1; it is
similar to the Method 5 train except the Filter
position is interchangeable. The sampling
train consists of the following components:
  5.1.1  Probe Nozzle. Pitot Tube,
Differential Pressure Caug*. Filter Heating
System, Metering System, Barometer, and
Gas Density Determination Equipment
Same as Method 5. Sections 2.1.1. 2.1.3. 2.1.4.
2.1.6, 2.1.8, 2.1.9. and 2.1.10. When moisture
condensation is a problem, the filter heating
system is used.
  5.1.2  Probe Liner.  Borasilicate glass or
316 stainless steel. When the filter is located
immediately after the prob«. the tester may
use a prob« beating system to prevent filter
plugging resulting from moisture
condensation, but the tester shall not allow
the temperature in the probe to exceed
120±14*C (248±25'F)-
  5.14  Filter Holder.  With positive seal
•gainst leakage from the outside or around
the filter.'If the  filter is located between the
probe and first  impinger. use borosilicate
glass or stainless steel with  a 20-mesh
stainless steel screen filter support and a
silicone rubber gasket: do not use a  glass frit
or a sintered metal filter support. If the filter
is located between the third and-fourth
impingers. the tester may use borosilicate
glas* with a glass frit filter support and a
silicone rubber gasket. The tester may also
use other materials  of construction with
approval from the Administrator.
  5.1.4  Impingers.   Four impingers
connected as shown in Figure 13A-1 with
ground-glass (or equivalent), vacuum-tight
fittings. For the first third .and fourth
impingers, use the Greenburg-Smith design.
modified by replacing the tip with a U-cm-
inside-diameter (V*  in.) glass tube extending
to 1.3 on (V4 in.) from the bottom of the flask.
For the second  impinger. use a Greenburg-
Smith impinger with the standard tip. The
tester may use modifications (e.g., flexible
connections between the impingers  or
materials other than glass), subject to the
approval of the Administrator. Place a
thermometer, capable of measuring
temperature to  within i*C (2'F). at the outlet
of the fourth impinger for monitoring
purposes.
  5.2  Sample Recovery. Th'e following
items are needed:
  5.2.1  Probe-Liner and Probe-Nozzle
Brushes, Wash  Bottles. Graduated Cylinder
and/or Balance. Plastic Storage Containers.
Rubber Policeman. Funnel  Same as Method
5. Sections 2^.1 to 2i2 and  2^.5 to 2.2.8,
respectively.'
         Sample Storage Container.  Wide-
 mouth, higb-density-polyetbylene bottles for
 impinger water samples, 1-liter.
   5.3  Analysis.  The following equipment is
 needed:
   5.3.1  Distillation Apparatus.  Glass
 distillation apparatus assembled as shown in
 Figure 13A-2.
   5.3.2  Bunsen Burner.
   5.3.3  Electric Muffle Furnace,  Capable of
 heating to 600'C.
   5.3.4  Crucibles.  Nickel. 75- to 100-mL
   5.3.5  Beakers.  500-ml and 1500-ml
   5.3.6  Volumetric Flasks.  50-ml.
   5.3.7  Erlenmeyer Flasks or Plastic Bottles.-
 500-ml
   5.3.8  Constant Temperature Bath.
 Capable of maintaining a constant
 temperature of ±1.0*C at room temperature
 conditions.
   5.3.9   Balance.  300-g capacity to measure
 to ±0.5 g.
   5.3.10  Spectrophotometer.  Instrument
 that measures absorbance at 570 nm and
 provides at least a 1-cm light path.
   5J.il  Spectrophotometer Cells.  1-cm
 patnlength.

 6. Reagents
   6.1  Sampling.  Use ACS reagent-grade
 chemicals or equivalent unless otherwise
 specified. The reagents used in sampling an
 as follows:
   6.1.1  Filters.
   6.1.1.1  If the filter is located between the
 third and fourth impingers, use a Whatman'
 No. 1 filter, or equivalent sized to fit the filter
 bolder.

 BILLING COOe t MO-01-M
  1 Mention of company or product ntmn do«i net
constitute endorsement by the U.S. Environmental
Protection Agency.
                                                                                                                iff
              from  Federal  Register.  Vol.  45,   No.   121,  pp.  41852-41857,
   Friday,   June  20,   198"6T

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                                        Section No.  3.10.16
                                        Revision No.  0
                                        Date January  4, 1902
                                        Page 2  of 5
 TttinRATURt
 • u-innMi wnc  •         !»••—«•«»•••«»
   ««OR     STACK MALI  | OPTIONAL HLTIRJ
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                                                                    o
                                            THtRUOUnCR

                                                  CHICK VALVI
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                                              VACUUM tAUel
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                                                                        O
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                  \
                       CONOtttUR
 Fi^uro 13A-2. Fluorldt dlnlllition ipparnua.
cess ea-avc
                                                                    O

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  CO.U  If Ibe filler is located between the
probe and first impinger, use any suitable
medium (e.g., paper organic membrane) that
conforms to the following specifications: (1)
The filter can withstand prolonged exposure
to temperatures up to IIS'C (275'F)- (2) The
filter has at least SS percent collection
efficiency (O percent penetration) for OJ pm
dioctyl phlhalate smoke partides. Conduct
the filter efficiency test before the test series.
using ASTM Standard Method D 2986-71. or
use teit data from the supplier's qualify
control program. (3) The filter has a low F
blank value (<0.01S mg F/cm* of filter area).
Before the test series, determine the average
F blank value pf at least three filters (from
the lot to be used for sampling) using the
applicable procedures described in Sections
7J and 7.4 of this method. In general, glass
fiber filters  have high and/or variable F
blank values, and will not be acceptable for
use.
  6.1.2 Water.  Deionized distilled, io
conform to ASTM Specification 01193-74,
Type 3. If high  concentrations of organic
matter are not expected to be present the
analyst may delete the potassium
permanganate test for oxidizable organic
matter.
  8.1.J Sflica  Gel. Crushed Ice, and
Stopcock Crease. Same as Method 5.
Section 3.1,2.3.1.4, and S/LS. respectively.
  &£  Sample Recovery.  Water, from same
container as described in Section 8.1.2. is
needed for sample recovery.
  8.3  Sample Preparation and Analysis.
The reagents needed for sample preparation
and analysis are as follows:
  6.3.1 Caldum Oxide (CsO). Certified
grade containing 0.005 percent F or less.
  8.3.2 Phenolphthalein Indicator.
Dissolve OJ g of pbenolphthalein in a mixture
of SO ml of 80 percent ethane! and SO ml of
deionized distilled water.
  6J.3 Silver Sulfate (Ag^O,).
  6.3.4  Sodium Hydroxide (NaOH).
Pellets.
  6.3J Sulfuric Add (HtSOO. Concentrated.
  6.3.6 Sulfuric Add. 25 percent (V/V).
Mix 1 part of concentrated H.SO. with 3
pans of deionited distilled water.
  6-3.7 Filters.  Whatman No. 541. or
equivalent
  6JJ Hydrochloric Add (HC1).
Concentrated.
  £L3.fl Water.  From same container as
described in Section 6.1.2.
  6.3.10  Fluoride Standard Solution. 0.01 mg
F/mL  Dry in an oven at 110'C for at least 2
hours. Dissolve 0.2210 g of NaF in 1 liter of
deionized distilled water. Dilute 100 ml of this
solution to 1 liter with deionized distilled
water.
  6J.11  SPADNS Solution [4. 5 dihydroxy-3-
(p-«ulfophenylazo}-2.7-naphthalene-disulfonic
acid trisodium s*ll].  Ditsolve 0.980 ± 0.010
g of SPADNS reagent in 500 ml deionized
distilled water. If stored in  a well-tealed
bottle protected from the sunlight this
solution is stable for at least 1 month.
  6.3.12  Spectrophotomeler Zero Reference
Solution.  Prepare daily. Add 10 ml of
SPADNS solution (6J.11) to 100ml deionized
distilled water, and acidify with a solution
prepared by diluting 7 ml of concentrated HC1
to 10 ml with deionized distilled water.
  6-3.13  SPADNS Mixed Reagent  Dissolve
0.135 ± 0.005 g of zirccny] chloride
octahydrale (ZrOCU. ZHJ3) in 25 ml of
deionized distilled water. Add 350 ml of
concentrated HC1. and dilute to 500 ml with
deionized distilled water. Mix equal volumes
of this solution and SPADNS solution to form
a single reagent This reagent is stable for at
least 2 months.

7, Proccdtm
  7.1  Sampling.  Because of the complexity
of this method, testers should be trained and
experienced with the text procedures to
assure reliable results.
  7.1.1  Pretest Preparation.  Follow the
general procedure given in  Method 5. Section
4.1.1. except the filter need  not be weighed.
  7.12  Preliminary Determinations.
Follow the general procedure given in
Method 5. Section 4.1A. except  the nozzle
size selected must maintain isokiaetie
sampling rates below 28 liters/min (LO din).
  7.14  Prepara tion of Collection Train.
Follow the general procedure given in
Method S, Section 4.1 J. except lor the
following variations:
  Place 100 ml of deionized distilled water in
each of the first two impingers. and leave the
third impinger empty. Transfer approximately
200 to 300 g of preweighed silica gel from its
container to the fourth impinger.
 sAssemble the train as shown  in Figure
13A-1 with the filter between the third and
fourth impingers. Alternatively, if a-20-mesb
stainlest steel screen is used for the filter
support the tester may place the Cher
between the probe and first impinger. The
tester may also use a filler  heating system to
prevent moisture condensation, but shall not
allow the temperature around the filter bolder
to exceed 120 ± 14'C (24* * 25'F). Record
the filter location oa tha data sheet
  7.14  Leak-Check Procedures.  Follow the
leak-check procedures given in Method 5,
Sections 4.1.1.1 (Pretest Leak-Check). 4.1.4.2
(Leak-Checks During the Sample Run), and
4.1.4J (Post-Test Leak-Check).
  7J_5  Fluoride Train Opera lion.  Follow
the general procedure given in Method 5,
Section 4.1 £, keeping the filter and probe
temperaturet (if applicable) at 120 ± U'C
(243 :± 25*F) and isokinetic sampling rates
below 28 liters/min (1.0 cfm). For each run.
record the data required  on a data sheet tuch
as the one shown in Method 5. Figure 5-2.
  7.2  Sample Recovery.  Begin proper
deanup procedure as soon as the probe is
removed from the stack at the end of the
sampling period.
  Allow the probe to cool!  When it can be
safely handled, wipe off  all external
particulate matter near the tip of the probe
nozzle and place a cap over it to keep from
losing part of the sample. Do not cap off the
probe tip tightly while the sampling train it
cooling down, because a vacuum would fora
in the filter holder, thus drawing iapinger
water backward.
  Before moving the sample train to the
cleanup site, remove the probe from the
sample train, wipe off the silicone grease, and
cap the open outlet of the probe. Be careful
not to lose any condensate. if present.
Remove the filter assembly, wipe off the
silicons grease from-the filter bolder inlet.
Section No.   3.10.10
Revision  No.  0
Date  January  4,   1982
Page  3   of  5

and cap this inlet Remove the umbilical cerd
from the last impinger. and cap the impinger.
After wiping off the sittcone greet*, up off'
the filter holder ouUtt end any open impinge*
inlets and outlet*. The tetter may use ground-
glau stoppers, plastic caps, or serum caps to
dote these openings.
  Transfer the probe and Clter-implnger
assembly to an ana that Is clam and
protected from the wind so that the chances
of contaminating or losing the "simple is
minimized*
  Inspect the train before and duriag
disassembly, and note any abnormal
conditions. Treat the samples as follows:
  7.2.1  Container No. 1 (Probe, Filler, and
Impinger Catches).  Using a graduated
cylinder, measure to the nearest mi and
record the volume of th* water in the first
three impingers; include any condensate in
the probe in this determination. Transfer the
impinger water from the graduated cylinder
Into this polyethyleaa container. Add the
Rlter to this container. [The Elter may be
handled separately using procedures subject
to the Administrator'* approval.) Talcing can
that dust on the outside of the probe or other
exterior surfaces does not get into the
sample, clean all sample-exposed surfaces  •
(including the probe cms]*, probe fitting.
probe liner, first three impingers, impinger
connectors, and filter Bolder) with deiomztd
distilled water. Use less than 500 ml for the
entire wash. Add the washings io the sampler
container. Perform the deionized distilled
water rinses as follows:
  Carefully remove the probe nozzle and
rinse the inside surface with deionized
distilled water from a wash bottle. Brush with
a Nylon bristle brush, and rinse until the
rinse shows no visible particles, alter which
make a final rinse of this inside surface. Brush
and rinse the inside parts of the Swagelok
fitting with deionizad distilled water la a
similar way.
  Rinse the probe Easr wtth deionized
distilled water. While (quirting the water into
the upper end of the probe, tilt and rotate the
probe so that all inside surfaces will be
wetted with water. Let the water drain from
the lower end into the cample container. The
tester may use a funnel {glass or
polyethylene] to aid in transferring the liquid
washes to the container. Follow the rinse
with a probe brush. Hold the probe in an
inclined position, and squirt deionized
distilled witer into the upper end as the
probe brush is being pushed with a.twisting
action through the probe. Hold the tamplt
container underneath the lower end of the
probe, and catch any water and particulate
matter that is brushed from the probe. Run
the brush through the probe three times or
more. With stainless steel or other metal
probes, run the brush through in the above
prescribed manner at least six times since
metal probei have small crevices in which
paniculate matter can be entrapped. Rinse
the bruth with deionized distilled water, and
quantitatively collect these washings in the
 sample container. After the brushing, make a
final rinse of the probe as described above.
  It it recommended that two people dean
the probe to minimize sample losses.
Between sampling runs, keep brushes dean
and protected from contamination.

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                                                                                        Section  No.   3.10.10
                                                                                        Revision No.   0
                                                                                        Date  January   4,   1982
                                                                                        Page  4  of  5
                                                                                    o
  Rinse the Iniide surface of each of the Tint
 three impingers (and connecting glassware)
 three separate times. Use a small portion of
 deionized distilled water for each rinse, and
 brush each sample-exposed surface with a
 Nylon bristle brush, to ensure recovery of
 fine paniculate matter. Make a final rinse of
 •ich  surface and of the brush.
  After ensuring that all Joints have been
 wiped clean of the silicone grease, brush and
 rinse with deionized distilled water the inside
 of the Miter holder (front-half only, if filter Is
 positioned between the third and fourth
 impingers). Brush and rinse each surface
 three times or more if needed. Make a final
 rinse of the brush and filter holder.
  After all water washings and paniculate
 matter hive been collected in the sample
 container, tighten the lid so that water will
 not leak out when it ta shipped to the
 laboratory. Mark the height of the fluid level
 to determine whether leakage ocean during
 transport Label the container clearly to
 identify Its contents.
  73-2  Container No. 2 (Sample Blank).
 Prepare a blank by placing an unused filter in
 a polyethylene container and adding a
 volume of water equal to the total volume in
 Container No. 1. Process the blank in the
 same manner as for Container No. 1.
  7.2.3  Containerffo< 3 (Silica  Gel).  Note
 the color ofibe indicating silica gel to
' determine whether II has been completely
 spent and make a notation of its condition.
 Transfer the silica gel from the fourth
 irapinger to its original container and seal
 The tester may use  a funnel to pour the silica
 gel and a  rubber policeman to remove the
 silica gel from the impinge:. It is not
 necessary to remove the small amount of dust
 particles that may adhere to the irapinger
 wall  and are difficult to remove. Since the
 gain in weight Is to  be used for moisture
 calculations, do not use any water or other
 liquids to transfer the silica gel. If a balance
 Is available in the Meld, the tester may follow
 the analytical procedure for Container No. 3'
 in  Section 7.4.2.
  7.3  Sample Preparation and Distillation.
 [Note the liquid levels in Containers No. 1
 and No. 2 and confirm on the analysis sheet
 whether or not leakage occurred during
 transport. If noticeable leakage had occurred,
 either void the sample or use methods,
 subject to the approval of the Administrator,
 to  correct the final results.) Treat the contents
 of  each sample container as described below;
   7.3,1  Container No. 1 (Probe, Filter, and
 Impinger  Catches).  Filter this container's
 contents,  including  the sampling filler,'
 through Whatman No. Ml filter paper, or
 equivalent into a 1500-mJ beaker.
   7.3.1.1  If the filtrate volume exceeds 900
 ml. make  the filtrate basic (red to
 phenolphtbaleln) with NaOH, and evaporate
 to  less than 900 ml.
   7.3.1.2  Place the filtered material
 (including sampling filter) In a nickel crucible.
 add a few ml of deionized distilled water.
 and macerate the filters with a glass rod.
   Add 100 mg CaO to the crucible, and mix
 the contents thoroughly to form a slurry. Add
 two drops of phenolphthalein indicator. Place
 the crucible in a hood under infrared lamps
 or on a hot plate at low beat. Evaporate the
 water completely. During the evaporation of
the water, keep the slurry basic (red to
phenolphthalein) to avoid loss of F. If the
indicator rums colorless (addic) during the
evaporation, add CaO until the color turns
red again.
  After evaporation of the water, place the
crucible on a hot plate under a hood and
slowly Increase the temperature until tha
Whatman No. Ml and sampling filters char. It
may take several hours to completely char
the filters.
  Place the crucible in a cold muffle furnace.
Gradually (to prevent smoking) increase the
temperature to 600'C ajid maintain until tha
contents are reduced to .an ash. Remove the
crucible from the furnace and allow to cool
  Add approximately 4 g of crushed NaOH to
the crucible and **t*- Return the crucible to
the muffle furnace, and fuss the sample for 10
minutes at COO'C.
  Remove the sample from tha furnaca, and
cool to ambient temperature. Using several
rinsings of warm deloniitd distilled water.
transfer the contents of tha crucible to tht
beaker containing the filtrate. To assure
complete sample removal, rinse finally with
two 20-ml portions of 23 percent HtSO* and
carefully add to the btaker. Mix wall, and
transfer to a l-lit«r volumetric flask. Dilute to
volume with  deionized distilled water, and
mix thoroughly. Allow any undissolved solids
to settle.
  7.3.2  Container No. 2 (Sample Blank).
Treat in the same manner as described in
Section 7J.I  above.
  7.3.3  Adjustment of Add/Water Ratio in
Distillation Flask. (Use a protective shield
when carrying out this procedure.) Place 400
ml of deionized distilled water in the
distillation flask, and add 200 ml of
concentrated H*SO«. (Caution: Observe
standard precautions when mixing HtSO<
with water. Slowly add the add to the flask
with constant swirling.) Add some toft glass
b«ads and several snail piece* of broken
glass tubing, and assemble th« apparatus as
shown in Figure 13A-2. Heat the flask until it
reaches a temperature of 175'C (o adjust the
add/water ratio for subsequent distillations.
Discard the distillate.
  7.3.4  Distillation.  Cool the contents of
the distillation flask to below 60'C. Pipet an
aliquot of sample containing less than 10.0 mg
F directly into  the distillation flask, and add
deionized distilled water to make a total
volume of 220 ml added to the distillation
Cask. (To estimate the appropriate aliquot
size, select an  aliquot of the solution and
treat as described in Section 7.4.1. This will
be an approximation of the F content because
of possible Interfering ions.) Note: If the
sample contains chloride, add 5 mg of AgiSO-
to the flask for every mg of chloride.
  Place a 250-ml volumetric flask at the
condenser exit Heat the flask as rapidly as
possible with a Bunsen burner, and collect all
the distillate up to 175'C. During heatup. play
the burner flame up and down the side of the
flask to prevent bumping. Conduct the
distillation as rapidly as possible (15 minutes
or less). Slow distillations have been found to
produce low F recoveries. Caution: Be careful
not to exceed 175*C to avoid causing H.SO,
to distill over.
   If F distillation in the mg range is to be
followed by a  distillation in the fractional mg
range, add-220 ml of deionized distilled water
and distill It over as in the add adjustment
step to remove residual F from the distillation
system.
  The tester nay use the add in the
distillation flask until there is ctrry-over of
interferences or poor F recovery. Check for
these every tenth distillation using a
deloniztd distilled water blank and t
standard solution. Change tht add whenever
the F recovery Is less than CO percent or th«
blank value exc**ds 0.1 fig/ml.
  7.4  Analysis.
  7.4.1  Containers No. lead No, 2.  After
distilling suitable aliquot* from Container*
No. 1 and No. 2 according to Sactioa 7.3,4,
dilute the distillate in th« volumetric flasks to
exactly 250 ml with delonixad distiH»d water.
and mix thoroughly. Pip«t a suitable aliquot
of each sample distillate (coataiaing 10 to 40
US F/ml) into • beaker, and dilut* to SO ml
with dalonizad distilled water. Us* tha taaa
aliquot size for the blank. Add 10 rnl of
SPADNS mixed reagent (6-3J3), and mix
thoroughly.
  After mixing, placa the sample in a
constant-temp«ratura bath containing tha
standard solutions (see Section ftj) for 30
minute* before reading the abtorbancs on th«
tpectropbotomater.
  Set the ip«ctrophotomettr to zero.
absorbanee at 570 run with th« rtferenoa       _
solution (63.12). and check tba             f~\
ipectrophoiometer calibration with the     f      )
standard solution. Determine th« *b*orb«fice\	y
of the sample*, and determine the
concentration from the calibration curve. If
the concentration doe* not faH within the
rang* of the calibration carve. r*p*at tha
'procedure using a different rlrj aliquot
  7.4.2  Container MX 3 (Sffiea G«l).  W*£>
the spent silica gel (or silica jd plus
implnger) to the nearest OJ j ustog a balanca.
The tetter may conduct this  sttp in the field.

A Calibration
  Maintain • laboratory log olaJl
calibrations.
  6.1 Sampling Train.   Calibrate the
sampling train components according to the
indicated sections in Method & Probe Nozzle
(Section 8.1): Pitot Tube (Section 5.2):
Metering System (Section SJfc Probe beater
(Section 5.4): Temperature Gauges (Section
5.5); Leak Check of Metering System (Section
5.6); tnd Barometer (Section 5,7).
  &2 Spectrophotometer.  Prepare tha
blank standard by adding 10 ml of SPADNS
mixed reagent to 60 ml of deionized distilled
water. Accurately prepare a series of
standards from the 0.01 mg F/rol standard
fluoride solution (6.3.10) by diluting 0.2.4.6,
8.10,12. and 14 ml lo 100 ml with  deionized
distilled water. Pipet 50 ml from each solution
and transfer each  to a separate 100-ml
beaker. Then add 10 ml of SPADNS mixed
reagent to each. These standards will contain
0,10, 20, 30, 40 50, 60, and 70 Mg F (0 to 1.4 ug/
ml), respectively.                         X~N.
  After mixing, place the reference standard^  ^
and reference solution in a constant       \     /
temperature bath for 30 minutes before    V—'
reading the absorbanee with the
spectrophotometer.'Adjust all samples to tfcia
sara* ttmpcratura bate* analyzic*.

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                                                                            Section  No.  3.10.10
                                                                            Revision  No.   0
                                                                            Date  January  4,   1982
                                                                            Page  5  of  5
  With the spectrophotometer at 570 am. use
the reference solution (64.12) to set the
absorbance to zero.
  Determine the absorbance of the
standards. Prepare a calibration curve by
plotting ftg F/50 ml versus-absorbanca-on
linear graph paper. Prepare the standard
curve initially and thereafter whenever the
SPADNS mixed reagent is newly made. Also,
run a calibration standard with each set of
samples and if it differs from the calibration
curve by ±2 percent prepare a new standard
curve.

R-CalculatJont
  Carry out calculations, retaining at least
one extra decimal figure beyond that of the
acquired data. Round off figures after final
calculation. Other forms of the equations may
be used provided that they yield equivalent
results.
  9.1 Nomenclature.
A« » Aliquot of distillate taken for color
    development ml.
At • Aliquot of total sample added to still,
    ml
Bw, » Water vapor in the gas stream,
    proportion by volume.
C, m Concentration of F in stack gas. tag/in',
    dry basis, corrected to standard
    conditions of 760 mm Hg (29.02 in. Hg)
    and 293'K (528'R)
                                         • F, - Total F In sample, mg.
                                          pg F » Concentration from the calibration
                                              curve, Mg.
                                          Tn - Absolute average dry gas meter
                                              temperature (see Figure 5-2 of Method 5),
                                              •K('R).
                                          T, •• Absolute average stack gat temperature
                                              (see Figure 5-2 of Method S). *K ('R).
                                          Vt - Volume of distillate collected, ml
                                          VoUt) « Volume of gas sample as measured
                                              by dry gas meter, corrected to standard
                                              conditions, dscm (dscf).
                                          V, « Total volume of F sample, after final
                                              dilution, ml.
                                                *• Volume of water vapor in the gas
                                              sample, corrected to standard conditions
                                              san(scf).
                                            0.2 Average Dry Gas Meter Temperature
                                          and Average Orifice Pressure Drop. See data
                                          sheet (Figure 5-2 of Method 5).
                                            BJ Dry Gas Volume. Calculate V.^ and
                                          adjust for leakage, if necessary, using the
                                          equation in section 64 of Method 5.
                                            9.4 Volume of Water Vapor and Moisture
                                          Content Calculate the volume of water vapor
                                          V.4M4) and moisture content Bin from the data
                                          obtained in this method (Figure 13A-1): use
                                          Equations 5-2 and 5-3 of Method  5.
                                             9.5 Concentration.
                                             9.5.1  Total Fluoride in Sample.  Calculate
                                          the amount of F in the sample using the
                                          following equation:

                                     F)
  9 S3.  Fluoride Concentration in Stack Gas. Determine the F concentration in the stack
 gas using the following equation:
              Xstd)
                                               Eq.  13A-E
Where:
K « 35.31 ftj/m> if VB(«4) is expressed in
    English units.
  «s 1.00 m'/m' if V.(^) is expressed in
    metric units.
  9.6 Isokinetic Vanation and Acceptable
Results.  Use Method 5, Sections 6.11 and
6.12.

10. Bibliography

  1. Bellack, Ervin. Simplified Fluoride
Distillation Method. Journal of the American
Water Works Association. 50:5300.1958.
  2. MJtchell. W. J., J. C. Suggs, and F. J.
Bergman. Collaborative Study of EPA method
13A and Method 13B. Publication No. EPA-
600/4-77-050. Environmental Protection
Agency. Research Triangle Park, North
Carolina. December 1977,
  3. Mitchell. W. J. end M. R. Midgeft
Adequacv of Sampling Trains and Analytical
Procedures Used for Fluoride. Atm. Environ.
J0.-865-872.1976.
                                                                                          P

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                                             Section No.  3.10.11
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 1 of 1
11.0  REFERENCES

     1.   Determination  of  Total  Fluoride  Emissions  from  Sta-
          tionary   Sources;   SPADNS   Zirconium  Lake  Method.
          Federal Register,  Vol. 45.  June 20, 1980.

     2.   Mitchell, W. J., J. C. Suggs, and F. J. Bergman.   Col-
          laborative  Study  of  EPA Method  13A  and Method  13B.
          EPA-600/4-77-050.

     3.   Martin,  R.   M.  Construction  Details  of  Isokinetic
          Source Sampling Equipment.  APTD-0581, USEPA, Air Pol-
          lution Control Office,  Research  Triangle Park,  North
          Carolina.  1971.

     4.   Rom, J. J.  Maintenance, Calibration,  and Operation of
          Isokinetic   Source   Sampling  Equipment.    APTD-0576.
          USEPA Office of Air  Programs,  Research Triangle Park,
          North Carolina.  1972.

ADDITIONAL REFERENCES

Standard  Methods for  the Examination  of Water and Wastewater,
PublishedjointlyEythe American Public Health  Association,
American  Water Works  Association  and Water Pollution  Control
Federation, 14th Edition  (1975).

MacLeod,  Kathryn E.,   and Howard  L.  Crist,  "Comparison of the
SPADNS  Zirconium Lake  and  Specific   Ion  Electrode Network  of
Fluoride  Determinations  in  Stack  Emission  Samples,"  Analytical
Chonictry 45:1272-1273.  1973.

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                                             Section No.  3.10.12
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 1 of 6
12.0  DATA FORMS
                                                             «
     Blank data  forms are provided  on the following  pages  for
the convenience  of the Handbook user.  Each blank  form has  the
customary  descriptive title  centered at  the  top of  the  page.
However,  the  section-page documentation  in the  top  right-hand
corner  of each  page of other sections has been  replaced with  a
number  in  the lower right-hand  corner that will enable the user
to identify  and refer to  a  similar  filled-in form in the text
section.   For example, Form  M13A-2.1 indicates that the form is
Figure 2.1 in Section 3.10.2 of the Method 13A Handbook.  Future
revisions of this form, if any,  can be documented by 2.1A,  2.IB,
etc.   Four of the blank forms (the  first  listed below) are  in-
cluded in this section.  Eighteen are in Section 3.9.12 as  shown
by the M13B following the form number.
 2.3A & B (M13B)
 2.4A & B (M13B)

 2.5 (M13B)

 2.6 (M13B)
 3.1 (M13B)
 4.1 (M13B)
 4.2 (M13B)
 4.3 (M13B)
     Title
Fluoride Calibration Curve Data Form
Method ISA Analytical Data Form
Analytical Balance Calibration Form
Control Sample Analytical Data Form
Procurement Log
Dry Gas Meter Calibration Data Form
(English and Metric units)
Posttest Meter Calibration Data Form
(English and Metric units)
Stack Temperature Sensor Calibration
Data Form
Nozzle Calibration Data Form
Pretest Sampling Checks
Nomograph Data Form
Fluoride Field Data Form
Sample Recovery and Integrity Data Form

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                                            Section No.  3.10.12
                                            Revision No.  0
                                            Date January 4,  1982
                                            Page 2 of 6
Form                     Title
4.4 (M13B)          Sample Label
4.5 (M13B)          On-Site Measurement Checklist
5.1 (M13B)          Posttest Calibration Checks
5.2 (M13B)          Fluoride Analytical Data Form
6.1A & 6. IB (M13B)  Fluoride Calculation Data Form
                    (English and Metric units)
8.2 (M13B)          Method 13B Checklist To Be Used by Audi torn
                                                                     o
                                                                     O

-------
Spectrophotometer number


Calibration date
                              Analyst
                        SPADNS mix date
Ambient temperature
          °C
Spectrophotometer set at 570 nm
 Bath temperature


	yes
Reference solution used to set zero absorbance


Absorbance readings:  	 10 ug 	
         40 ug

           0.7
          0.6
          0.5
       o


       °*  0.4
        *
       Ol
       (J
       c
       «O
       JQ

       o  0.3
       tfi
       .O
          0.2
          0.1
50 M9
   60 ug
                     10
    20
30     40
                                 yes
                            20 ug
   70 ug
50
60
                          ug of fluoride per 50 ml
Signature of Analyst _


Signature of Reviewer
                     no


                     no
          30  ug


          blank
70
                                          Quality Assurance Handbook M13A-2.1

-------
     Plant
     Date
            KETKOD 13A ANALYTICAL DATA FORM
                     Location
     Samples identifiable 	
     Ambient temperature 	
     Sample was concentrated
Analyst
yes
                            SPADNS mix date
                 no  All liquid levels at mark
yes
no
                                     Temperature of standards
Temperature of samples 	
yes  	 no  Solids fused and added to liquid
                                                            yes
                no
Sample
number









Sample
identi-
fication









Total ,
volume
of sample
before
distill.
(Vt), ml









Aliquot
of
sample
for
distill.
(At), ml.









mg of
chloride
per liter
of sample









rag of
silver
chloride
added









Sample
volume
from still
(Vd), ml









Aliquot
of sample
for analysis
(Ad), ml









Absorb.
of sample
at 570 nm
OD









M9 F
in sample









Total
weight
of FD
(Ft),
mg









 Total weight of fluoride in  sample  (F.)
            aControl  samples results must be between 19.6 ug and 20.4 ug for
             undistilled sample on 18.0 an 22.0 ug for distilled sample
Ft = 10
             Remarks:
Signature of analyst _
Signature of reviewer
                                                           Quality Assurance Handbook H13A-5.1
        o
                     o
                                                                       o

-------
Balance name
Number
Classification of standard weights

Date

0.5000 g

1.0000 g


10.0000 g

50.0000 g

100.0000 g

Analyst

                                        Quality Assurance Handbook M13A-5.2

-------
Plant
Analyst
Date of calibration curve
      Date of analyfeis
      Ambient temperature
Temp, of calibration curve
o
Control sample temperature

Absorbance of control sample

Amount of F in control sample
  from calibration curve

Percent error between measured
  and calculated concentration
                                        Concentration of control sample
                                        Distilled
                  Undistilled
Were acceptable results obtained .on control samples (less than 2% undis-
tilled and <10% distilled)  	
                                                                                    O
                         Signature of analyst
                         Signature of reviewer
                                          Quality Assurance Handbook M13A-5.3
                                           O

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                                             Section No.  3.11
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 1 of 13
                           Section 3.11

     METHOD 17—DETERMINATION OF PARTICULATE EMISSIONS FROM
         STATIONARY SOURCES (IN-STACK FILTRATION METHOD)
                             OUTLINE
          Section
               Number of
Documentation    pages
SUMMARY
METHOD HIGHLIGHTS
METHOD DESCRIPTION
     1.   PROCUREMENT OF APPARATUS
          AND SUPPLIES
     2.   CALIBRATION OF APPARATUS
     3.   PRESAMPLING OPERATIONS
     4.   ON-SITE MEASUREMENTS
     5.   POSTSAMPLING OPERATIONS
     6.   CALCULATIONS
     7.   MAINTENANCE
     8.   AUDITING PROCEDURE
     9.   RECOMMENDED STANDARDS FOR
          ESTABLISHING TRACEABILITY
    10.   REFERENCE METHOD
    11.   REFERENCES
    12.   DATA FORMS
    3.11
    3.11
 2
10
3.11.1
3.11.2
3.11.3
3.11.4
3.11.5
3.11.6
3.11.7
3.11.8
3.11.9
3.11.10
3.11.11
3.11.12
9
2
3
6
1
1
2
2
1
11
1
1
                                                         Ci

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                                             Section No.  3.11
                                             Revision No. 0
                                             Date January 4, 1S82
                                             Page 2 of 13
                                                                o
                             SUMMARY
     EPA Method 17 consists  of procedures  for the determination
of particulate emissions  from  stationary  sources where particu-
late matter concentrations, over the normal range of temperature
associated with  a source category, are known  to be independent
of temperature.
     This method,  designed to be  used in conjunction  with EPA
Methods 1,  2,  3,  and  4,  describes an  in-stack sampling system
along with proper sampling and analytical procedures.
     A gas  sample is  extracted  isokinetically from the source.
Particulate matter is  collected on  a glass fiber  filter main-
tained at stack  temperature.   The  mass of particulate matter is
determined  gravimetrically after  removal  of  uncombined water.
     Particulate matter is  not an  absolute quantity; rather, it
is  a  function of  temperature  and  pressure.   Therefore, to pre-
vent  variability  in  particulate  matter  emission  regulations
and/or associated  test methods,  the temperature and pressure at
which  particulate matter  is to be  measured  must  be carefully
defined.  Of the two variables (i.e., temperature and pressure),
temperature has  the greater effect upon  the amount of particu-
late matter in an  effluent gas stream; in most stationary source
categories, the  effect  of pressure  appears to  be negligible.
     In  Method 5  a  temperature of  250°  F is  established  as  a
nominal  reference temperature.  Thus,  where Method 5 is speci-
fied  in  an applicable  subpart of  the  standards,  particulate
matter  is  defined with  respect  to  temperature.    In  order to
maintain  a  collection  temperature  of 250° F, Method 5  employs  a
heated  glass   sample  probe  and a heated filter  holder.   This
equipment is somewhat  cumbersome and requires  care in its opera-
tion.   Therefore,  where particulate matter concentrations  (over
the normal range of  temperature  associated with  a  specified
source  category)  are known to be  independent  of temperature, it

-------
                                             Section No. 3.11
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 3 of 13

is desirable  to eliminate the glass probe  and heating systems,
and sample at stack temperature.
     This  method  describes  an   in-stack   sampling  system  and
sampling procedures for use in such cases.   It is intended to be
used only  when specified by an  applicable  subpart of the stan-
dards,   and only within  the  applicable  temperature  limits  (if
specified),  or when  otherwise  approved by  the  administrator.
     This method is not applicable to stacks that contain liquid
droplets or  are. saturated with  water vapor.   In  addition,  this
method  shall not be  used as written if the projected cross-sec-
tional area of the probe extension filter holder assembly covers
more than 5% of the stack cross-sectional area.
     The Method Description which follows is based on the Refer-
ence Method that was promulgated on February 23, 1978.a
Note;   Due  to similarities between Method  5  and  Method 17 sam-
pling and  analytical  equipment and procedures, only the differ-
ences pertaining  to  Method 17 will be presented.   However,  the
activity matrices  are all  included whether  or  not differences
occur in the written descriptions.  All other Method 17 descrip-
tions will  be  referenced to  the corresponding  description in
Section 3.4,  Method. 5.   This  is done for  both time savings to
the reader and cost savings to the Government.

-------
                                             Section No. 3.11
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 4 of 13
o
                        METHOD HIGHLIGHTS

     Specifications for Method  17  and Method 5 are very similar
with respect to calibration, sampling and analytical procedures.
The two most significant items of concern with Method 17 are the
filter holder design and the determination of method applicabil-
ity.  The  main reason for the  problems  with the filter holders
is that there  are no design specifications stated for this ref-
erence method.  As  a result,  several different commercial types
of  filter  holders exist on  the market  to  date.   Most of these
have  some  of the problems  listed below  and should be checked:
     1.   Filter  holders do  not remain leakless over the normal       ^^^
range of temperature changes.                                          f  )
     2.   Filters  do not seal  properly with  the  filter holder
and allow particulate to circumvent the filter.
     3.   Filter  holders  tear  the  filter during assembly prior
to testing.
     4.   Particle  penetration  is suspected  with  some types of
filter holders  due to a very high  face  velocity at the filter.
     5.   Filter  cannot be  easily  removed  from  filter, holder
during sample recovery.
     6.   Filter  holder  gasket material  is unable to withstand
upper temperature limits of normal testing  range.
     7.   Filter  holder  design makes assembly  and disassembly
difficult.
     8.   Excess  weight  of  filter holder  causes  probe  sag in
the stack.
     9.   Large  diameter  of some  filter holders prevents their
use in a 3 in. diameter port.
    10.   Some  filter holders  - have  a  poor  design  for sample
recovery.
  O

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                                             Section No.  3.11
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 5 of 13

     Procedures for checking some of the problems have been pro-
vided in the method writeup.  The remaining problems can only be
detected by using the filter holders in the field.
     The  second most  significant  concern is determining  when
Method 17  is applicable.   Since  the  in-stack filtration method
was one  of the first particulate methods  used and is generally
easier to  use,  it  has  remained popular.  Method  17 is currently
being  substituted   for  Method  5  under  certain   conditions  for
compliance  determination  with State  and  local  air  pollution
regulations.   The  New  Source  Performance Standards  (NSPS)  de-
fines when Method  17 can  be used.   However, a  large number of
requests are being  made to substitute Method 17  for Method 5 on
NSPS performance tests.
     Depending  on   stack condition  and pollutant composition,
Method 17  results  can  easily vary  from as  little as 10 percent
to as much as  200  percent in comparison to Method 5.  Method 17
and Method  5 are not equivalent methods for many source catego-
ries,  because  the  temperature at which the  particulate  is col-
lected can have a  significant effect on the amount of particu-
late matter collected.   Method 17  and  Method 5  are equivalent
generally  only when the particulate matter is   independent of
temperature through the range of emission testing.  As a rule of
thumb, the filter  that  is  at  a  lower  temperature (in-stack or
out-of-stack) will  give equal  or  higher results  than the filter
at the higher temperature.
     The equivalency of Method 17 versus Method  5 may not even
be considered by the agency when allowing the use of Method 17.
The prime  consideration may be the  agency's legal definition of
particulate  matter.  As  an example,  if  sulfuric acid  is  not
considered  as  particulate matter from  power plants,  the agency
may allow  the  use  of Method 17 on  power plants  using even high
sulfur coal.   The  use  of  Method 17 in this case may  yield a
lower measured  emission rate value, but may be  legally accept-
able.

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                                             Section No.  3.11
                                             Revision No.  0
                                             Date January 4,  1982     ^^
                                             Page 6 of 13             (  J

     Method 17 does not have any special operational problems or
biases if  all the prescribed procedures  and specifications  are
followed.  As  with Method 5, the most  significant errors asso-
ciated  with  this method  occur  during  sample collection  and
recovery  phase.   Therefore,  this  method  requires  competent
personnel adhering to  the  procedures.   Competence can be deter-
mined, most accurately,  through observation and evaluation by a
qualified observer onsite.                     ,
     The blank data  forms at  the  end of this section  may be
removed  from  the  Handbook and used  in the pretest,  test,  and
posttest operations.  Each form has a subtitle  (e.g., Method 17,
Figure 3.1) to  assist the user in finding  a  similar filled-in
form in the method description  (e.g., in Section 3.4.3 of Method
5).  Only  those forms  that are different from those in Method 5
are  included  at  the  end  of  this  section.  On the  blank  and      /~\
filled-in  forms,  the  items/parameters  that can cause the most      \	}
significant errors are designated with an asterisk.
1.   Procurement of Equipment
     Section 3.11.1  (Procurement  of  Apparatus  and  Supplies)
gives  the  specifications,  criteria  and  design   features  for
equipment and materials  required for performing Method 17 tests.
Special  design  criteria  have  been  established for  the pitot
tube, nozzle, and temperature sensor assembly.
     These  criteria  specify the necessary spacing requirements
for  the  various components  of the assembly  to prevent  aerody-
namic  interferences that  could cause large  errors in velocity
pressure measurement.   Special attention  has  been paid to pro-
viding a detailed procedure  for determining  if  the  filter holder
design  is  sufficient to  remain leak  free through  the normal
range of testing temperatures.
      Section  3.11.1  is designed as  a guide for the procurement
and  initial  check  of  equipment  and  supplies.   The activity
matrix  (Table  1.1) at  the  end  of Section 3.11.1 can be used  as  a
quick reference;  it  follows the same order as the written de-
ccription  in  the main  text.                                 'I?^'
o

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                                             Section No.  3.11
                                             Revision No.  0
                                             Date January 4,  1982
                                             Page 7 of 13
2.   Pretest Preparation
     Section 3.11.2  (Calibration of Apparatus)  is  the same  as
the calibration section for Method 5 (Section 3.4.2).
     Section 3.11.3 (Presampling Operations) provides the tester
with a  guide for  supplies  and equipment preparation  for field
tests.   The pretest preparation form can be used as an equipment
checkout and  packing list.   (Due to the  length  of this figure,
the blank data form is given only in Section 3.4.3, Figure 3.2).
This form  was designed to  provide the user with  a single form
that can include  any combination  of  Methods 1  through  8  and
Method  17  for the same field trip.  The  method  for packing and
the  description  of packing containers should help  protect the
equipment,  but are not mandatory.  Filter holders and impingers
may  be  loaded and  charged  in the  base laboratory.   If this is
done, seal  the inlet  and  outlet of the  filter  holder,  the im-
pingers  containing water,  and  the impinger  containing  silica
gel.
3.   On-site Measurements
     Section  3.11.4 (On-site Measurements) contains  a step-by-
step  procedure  for  performing  sampling  and sample  recovery.
Several  on-site  measurement requirements have been added which
will  significantly improve  the  accuracy  and precision  of the
method.  These added requirements include:
     1.   Do not use this method for saturated stacks .with water
droplets,
     2.   Make a  corresponding change  in  the sampling rate when
velocity pressure  at each sampling point changes by >20%,
     3.   Leak check the sampling train at the conclusion of the
sampling run  and  prior to each component change during a sample
run,
     4.   Leak check the pitot  tube  at  the conclusion  of the
sampling run,

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                                             Section No.  3.11
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 8 of 13

     5.   Have one  traverse  diameter in  a  plane containing  the
greatest expected concentration variation, and
     6.   Allow sufficient time for the filter holder to equili-
brate with the stack temperature.
The  on-site  measurement  checklist (Figure 4.5) is  provided to
assist the tester with  a quick method of checking requirements.
4.   Posttest Operations
     Section 3.11.5 (Postsampling Operations) gives the posttest
equipment check procedures and a step-by-step analytical proce-
dure.  Figure 5.1 of Section 3.4.5, or a similar form, should be
used to  summarize the posttest calibration checks and should be
included in the emission test report.
     The posttest  operation  forms  (Figures 5.5  and 5.6  of Sec-
tion 3.4.5) will provide laboratory personnel with a summary of
analytical procedures  used  to determine  the sample  rinse  and
filter weights.   This  analytical  procedure is the  same as  for
Method 5 (Section 3.4.5).
     Section  3.11.6  (Calculations)  is  the same  as Method  5
(Section 3.4.6).
     Section  3.11.7 (Maintenance) supplies  the tester  with  a
guide for a routine maintenance program.  The maintenance of the
in-stack filter holder  is the only item different than Method 5
(Section 3.4.7).
5.   Auditing Procedures
     Section 3.11.8 (Auditing Procedures) contains a  description
of  necessary activities  for conducting  performance and system
audits.  The performance  audit is  a check on calculation errors,
and  therefore  is not needed for  the  analytical phase since it
consists of  only  a gravimetric determination.   Together, a per-
formance audit  of data  processing and  a  system  audit of on-site
measurements  should provide the  independent assessment of data
quality  needed to  allow the  collaborative  test  results to be
used in  the final data evaluation.
o

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                                             Section No.  3.11
                                             Revision No.  0
                                             Date January 4,  1982
                                             Page 9 of 13
6.   References
     Section  3.11.9  (Recommended  Standards  for  Establishing
Traceability)  recommends  the  primary  standards  to  which  the
sample collection and analysis should be traceable.
     Section 3.11.10 is the Reference Method and 3.11.11 (Refer-
ences)  lists the  references used  in  the  compilation of  this
ccction of the Handbook.

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                                                      Section No.  3.11
                                                      Revision No.  0
                                                      Date  January 4, 1982
                                                      Page  10 of  13
                                             o
                           PRETEST SAMPLING CHECKS
                           (Method 17, Figure 3.1)
Date
Meter box number
Calibrated by
Dry Gas Meter*

Pretest calibration factor Y
  tor for each calibration runT!

Impinger Thermometer

Was a pretest temperature correction  used?
  If yes, temperature correction  	

Dry Gas Meter Thermometers
         (within ±2% of the  average  fac-
                    yes
no
        (within ±3°C (5.4°F)  over  range)
Was a pretest temperature correction  made?     	 yes      	 no
  If yes, temperature correction	  (within ±3°C (5.4°F) over range)

Stack Temperature Sensor*
  »
Was the stack temperature sensor calibrated against  a reference thermometer?
  	yes  	  no
  If yes, give temperature range with which the  readings agreed within ±1.5%
  of the reference values 	 to 	K  (°R)
Barometer
Was the pretest field barometer reading correct?
                      yes
no
   (within ±2.5 mm (0.1 in.) Hg of the mercury-in-glass  barometer)

Nozzle*

Was the nozzle calibrated to the nearest 0.025  mm (0.001  in.)?
   	yes  	 no
        O
                                                                                   o
 *Most  significant items/parameters to be checked.

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                                                     Section No.  3.11
                                                     Revision  No. 0
                                                     Date January 4,  1982
                                                     Page 11 of 13
                         ON-SITE  MEASUREMENTS CHECKLIST
                             (Method  17,  Figure 4.5)
Apparatus
Probe nozzle:  stainless steel	  glass
  Button-hook	 elbow	  size
  Clean?
Pi tot tube:   Type S	  other
  Properly attached to probe?*  IHIIIZZZZZZZI	
  Modifications
  Pi tot tube coefficient
Differential pressure gauge:   two  inclined manometers
  other 	   sensitivity
Filter holder:   borosilicate  glass 	 stainless steel
  Clean?
Condenser:  number of impingers
  Clean?
  Contents:   1st 	  2nd 	  3rd 	  4-th
  Cooling system
  Proper connections?
  Modifications
Barometer:  mercury	  aneroid 	  other
Gas density determination:   temperature  sensor type 	
  pressure gauge
  temperature sensor properly  attached  to probe?*  	

Procedure

Recent calibration:   pitot tubes*	
  meter box* 	  thermometers/thermocouples*
Filters checked visually for irregularities?*  	
Filters properly labeled?*
Sampling site properly selected?
Nozzle size properly selected?*
Selection of sampling time?
All openings to sampling train  plugged  to prevent pretest contamination?

Impingers properly assembled?   IZIZIZZIZIZIZZZZZZZZZZZIIZIZIIIZZIIZI
Filter properly centered?
Pitot tube lines checked for plugging  or  leaks?*  	
Meter box leveled?  	  Periodically?
Manometers zeroed?
AH@ from most recent calibration
Nomograph setup properly?
Care taken to avoid scraping nipple  on  stack wall?*

(continued)

-------
                                                     Section  No. 3.11
                                                     Revision No.  0
                                                     Date January  4,  1982
                                                     Page 12  of- 13              /""\


(continued)

Effective seal  around probe  when  in-stack?  	
Filter holder allowed to equilibrate with stack temperature?  	
Probe moved at proper time?
Nozzle and pi tot tube parallel  to  stack wall at all times?*  ———————
  Filter changed during run?
  Any particulate lost?	
Data forms complete and data  properly  recorded?"'  IIZZZZZIIZIZIZZZIZZZIIZI
Nomograph setting changed  when  stack temp  changed significantly?

Velocity pressure and orifice pressure readings recorded accurately?*

Posttest leak check performed?*(mandatory)
Leakage rate  	      @ in. Hg                       	
  Orsat analysisfrom stack   	integrated
  Fyrite combustion analysis  	~sample location	
  Bag system leakchecked?*
  If data forms cannot be copied,  record:
    approximate stack temp	 volume metered
    % isokinetic calculated at end of  each  run
SAMPLE RECOVERY

Brushes:   nylon bristle	   other
  Clean?
                                                                                 o
Wash bottles:  glass
  Clean?
Storage containers:   borosilicate glass 	  other
  Clean?                               Leakfree?
Petri dishes:  glass              polyethylene	  other
  Clean?
Graduated cylinder/or balance:subdivisions  <2  ml?*
  other                                      ~"
  Balance:  type
Plastic storage containers:   airtight?
  Clean?
Probe allowed to cool sufficiently?	__
Cap placed over nozzle tip to prevent loss of  particulate?*
During sampling train disassembly,  are all  openings  capped?
Clean-up area description:
  Clean?                                Protected from wind?
Filters:  glass fiber	  type
  Silica gel:  type (6 to 16 mesh)?  new?    "	 used?
  Color?                                 Condition?
Filter handling:  tweezers used?
  surgical gloves?
  Any particulate spilled?*

(continued)
surgical  gloves?  	  other	       C  j

-------
                                                     Section No.  3.11
                                                     Revision No.  0
                                                     Date  January 4, 1982
                                                     Page  13 of  13
(continued)

Water distilled?	
Stopcock grease:   acetone-insoluble?  	
  heat-stable-silicone?  	  other
Particulate recovery from:  probe nozzle 	
  probe fitting
  front half of filter  holder
Blank:   acetone 	  distilled water
Any visible particles  on  filter holder?:* 	
All jars adequately labeled?   	  Sealed tightly?
  Liquid level  marked on  jars?*           "~	
  Locked up?
Acetone reagent:<0.001%  residue?
  glass bottles 	(required)
  acetone blanks?
*Most significant items/parameters to be checked.

-------
o
o
o

-------
                                             Section No. 3.11.1
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 1 of 9
1.0  PROCUREMENT OF APPARATUS AND SUPPLIES
     A  schematic  of  the  sampling  train used  in  Method  17  is
shown in Figure 1.1.  Commercial models of this train are avail-
able.   For those  who  want to  build  their own,  construction
details for many, but not all of the train components are given
in  APTD-0581.2  Allowable  modifications  are  described  in  the
following sections.
     The operating,  maintenance,  and calibrating procedures  for
the  sampling  train  are in  APTD-0576.3   Since  correct usage is
important  in  obtaining valid results,  all  users are advised to
read this  document  and adopt its procedures unless alternatives
are outlined herein.
     In this  section,  applicable specifications, criteria, and/
or  design  features  are given to aid  in the selection of equip-
ment or any components that are different from those in Section
3.4.1.  Procedures  and limits  (where applicable) for acceptance
checks are given.
     Table 1.1  at  the  end  of this section  is  a summary of the
quality assurance activities  for the procurement and acceptance
of apparatus and supplies.
1.1  Sampling Apparatus
1.1.1  Filter Holder  - An in-stack filter holder constructed of
borosilicate or quartz glass,  or stainless steel is required by
the Reference Method.   If a gasket is used, it should be made of
silicone  rubber,   Teflon,  or  stainless  steel.   Other  filter
holders and gasket materials may be used subject to the approval
of  the  administrator.  The holder  should be  durable,  easy to
load, and  leak free  in normal applications.   It  is positioned
immediately following  the nozzle,  with the filter placed toward
the flow.

-------
     »-/ fc 1.9 en  4
         (0.75 In.)
         i > 7.6 en
            (3 In.)
                                      IM-STACK
                                    FILTER HOLDER
r
  TYPE-S
PITOT  TU3E


      TEKPERATIHE
        SEHSOR
             \   >
    HOZZLE

  IH-STACK^
   FILTER
   HOLDER

   TYPE-S
   PITOT TUOE
                                                    IWIKGER TRAIN OPT1KWL, KAY CE REPLACED
                                                          Or A.1 EQUIVALENT
* SUGGESTED (IHTERFEREBCE-FREE)  SPACIKGS

       Figure  1.1.   Schematic of Method 17 sampling train.
                                                                                                                    YACUUH LIRE
                                                                                                                                  vQ
                                                                                                                                   (D
                                                                                                             a o
                                                                                                             < o
                                                                                                             srtt
                                                                                                         toc< p. o
                                                                                                           P) O ^
                                                                                                         O 3 CJ
                                                                                                                                    >.1 o
                                                                                                                                     in
                                                                                                                                     o>
                                                                                                                                     10
            O
                                            o
                                                                                               o

-------
                                             Section No. 3.11.1
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 3 of 9

     One of the biggest problems with the Method 17 train is the
inability of  some filter holders to  remain leakless during the
wide range  of temperatures for which they  are  used.  To ensure
that  each  filter holder  is properly  designed,  a leak  check
should be performed as follows:
     1.   Assemble the  sample probe, filter  holder, and filter
as shown  in Figure  1.1  with the exception  that a  steel plug or
blank should be  used in place of the nozzle  to provide a leak-
less  seal.   Note:   The condenser  section  does not have  to be
used.   However,  it  is  suggested that  it be used  to  provide a
more normal leak check  with regard to  the  amount  of air volume
that is removed  from the train and  all of  the  standard connec-
tions will  also be leak checked.
     2.   Perform the standard leak check  at 380  mm Hg (15 in.
Hg) vacuum  at ambient  temperature.   A  leakage  rate of 0.00057
m3/min  (0.02  ft3/rain)  is  allowed;  however,  under  these labora-
tory conditions the entire train should be leakless.
     3.   Put  the filter holder in an  oven  (a Method 5 filter
heater  compartment can be used) at about 100°C  (212°F) for about
30 min.  Perform the leak check with  the  filter  holder in the
oven.   The  filter holder should again remain leakless.
     4.   Remove  the filter holder  from the oven  and let cool
for 30  min.  Again run the leak check.
     5.   Place  the  filter  holder  in  the  oven at the maximum
temperature  for   which  you  plan to  use the Method  17 filter
holder.   Allow 30 min for the holder to reach  this temperature
and then run  the leak check.  Note:  This  may  require that the
gasket  material be changed to a high temperature material.
     6.   Remove the filter holder and let cool for 30 min.  Run
the final leak check.
     If the filter  holder passes  these leak  check procedures
then it is properly designed to remain leak free  when properly
maintained.  If  the  filter holder  passes the leak checks at the
lower  temperatures,  but not  the maximum temperature,  the manu-
facturer  may  have to be contacted  to either replace the filter
                                                           f lui. ST -

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                                             Section No. 3.11.1
                                             Revision No. 0
                                             Date January 4,  1982     /"""N
                                             Page 4 of 9              V_y

holder or provide  a  gasket that is designed for higher tempera-
ture sampling.  If the  filter holder is unable to pass the leak
check procedure  at 100°C return the holder  to the manufacturer
unless sampling is to be performed only at ambient temperature.
1.1.2  Probe Extension  -  Any  suitable  rigid probe extension may-
be used after the  filter holder.  After procuring a probe exten-
sion, the user should visually check it for specifications; that
is, is it the  length and composition ordered?  The probe exten-
sion  should be visually checked  for  cracks or breaks,  and it
should be checked for  leaks  on a sampling  train (Figure 1.1).
This includes a proper,  leak free filter holder to probe connec-
tion.   It  is  suggested that  when corrosive  gases  are present
during testing that the probe  extension  be  made  of stainlesc
steel.   The use  of  a  heated glass-lined  probe  should be con-        ^_^
sidered by the tester when corrosive or condensible material are       ()
present  in  the stack.    The  condensed  or  corroded  materials in
the probe extension may drain or be back flushed into the filter
and contaminate the sample.
1.1.3  Condenser - It is recommended that an impinger system de-
scribed  in  Method  5  (Section 3.4) be used to determine moisture
content  of  the  stack   gas.   Alternatively,  a  condenser  that
allows  the  measurement of  both  the  water  condensed  and  the
moisture leaving  the condenser,  each to within 1 ml or 1 g, (as
described in Section 3.4.1) may be used.
                                                                       o

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                                                      Section No. 3.11.1
                                                      Revision  No. 0
                                                      Date January 4,  1982
                                                      Page 5 of 9
     TABLE 1.1.   ACTIVITY MATRIX  FOR  PROCUREMENT OF APPARATUS AND SUPPLIES
Apparatus
Sampling

Probe nozzle
Filter holder
Probe extension
Pitot tube
Differential
  pressure
  gauge
  (manometer)
Impingers
Filter holder
  gasket
Acceptance limits
Stainless steel  (316)
or glass with sharp,
tapered angle <30°;
difference in measured
diameters <0.1 mm (0.004
in.); no nTcks,  dents,
or corrosion (Sec 3.4.1)
Leak free; borosilicate
or quartz glass or
stainless steel
Specified material  of
construction; correct
length (Sec 3.4.1)
Type S (Sec 3.1.2);
attached to probe with
impact (high pressure)
opening plane even with
or above nozzle entry
plane
Meets criteria (Sec
3.1.2); agree within
5% of gauge-oil
manometer (Sec 3.4.1)
Standard stock glass;
pressure drop not ex-
cessive (Sec 3.4.1)
Provide a leak free
seal on filters within
the suggested manufac-
turers temperature
range
Frequency and method
   of measurements
Visually check before
each test; use a mi-
crometer to measure
ID before field use
after each repair
Visually check before
use
Visually check for
cracks and breaks,
leak check
Calibrated according
to Sec 3.1.2
Check against a gauge-
oil manometer at a
minimum of 3 points:
0.64(0.025); 12.7
(0.5); 25.4(1.0) mm
(in.) H20
Visually check upon
receipt; check pres-
sure drop (Sec 3.4.1)
Upon receipt deter-
mine the acceptable
temperature range
for each gasket
material
Action if
requirements
are not met
Reshape and
sharpen, re-
turn to the
supplier, or
reject
Return to
supplier
Repair, re-
turn to sup-
plier, or re-
ject
Repair or re-
turn to sup-
plier
As above
Return to
supplier
Contact manu-
facturer to
determine
temperature
range
(contliu&d)

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                                                      Section No. 3.11.1
                                                      Revision No. 0
                                                      Date January 4,  1982
                                                      Page 6 of  9
Table 1.1 (continued)
Apparatus
Vacuum gauge
Vacuum pump
Orifice meter
Dry gas meter
Thermometers
Barometer
Acceptance limits
0-760 mm (0-30 in.) Hg
range, ±25 mm (1  in.)
at 380 mm (15 in.)' Hg
Leak free; capable of
maintaining a flow
rate of 0.02-0.03
mVmin (0.7 to 1.1
ftVmin) for pump
inlet vacuum of 380 mm
(15 in.) Hg
AH@ of 46.74 ± 6.35 mm
(1.84 ± 0.25 in.) H20
at 68°F (not mandatory)
Capable of measuring
volume within ±2% at <
flow rate of 0.02
mVmin (0.75 ftVmin)
±1°C (2°F) of true
value in the range of
0° to 25°C (32° to 77°F)
for impinger thermometer
and ±3°C (5.4°F) of true
value in the range of
0°C to 90°C (32° to
194°F) for dry gas
meter thermometers
Capable of measuring
atmospheric pressure
within ±2.5 mm (0.1
in.) Hg
Frequency and  method
   of measurements
Check against mer-
cury U-tube manometer
upon receipt
Check upon receipt
for leaks and capaci-
ty
Upon receipt,  visual-
ly check for damage
and calibrate  against
wet test meter
Check for damage upon
receipt and calibrate
(Sec 3.4.2) against
wet test meter
Check upon receipt
for dents or bent
stem, and calibrate
(Sec 3.4.2) against
mercury-in-glass
thermometer
Check against a mer-
cury-in-glass barom-
eter or equivalent;
calibrate (Sec 3.1.2)
Action if
requirements
are not met
Adjust'or re-
turn to sup-
plier
Repair or re-
turn to sup-
plier
Repair if
possible,
otherwise re-
turn to sup-
plier
Reject if
damaged, be-
haves errati-
cally, or
cannot be
properly ad-
justed
Reject if un-
able to cali-
brate
Determine
correction
factor, or
reject if
difference
more than
±2.5 mm (0.1
in.) Hg
                                                                                o
                                                                                 o
                                                                                 o
 (continued)

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                                                      Section No.  3.11.1
                                                      Revision No. 0
                                                      Date January 4,  1982
                                                      Page 7 of  9
Table 1.1 (continued)
Apparatus
Acceptance limits
Frequency and method
   of measurements
Action if
requirements
are not met
Sample Recovery

Filter holder
  and nozzle
  brush
Nylon bristle with
stainless steel  stem;
properly sized and
shaped
Visually check for
damage upon receipt
Replace or
return to
supplier
Wash bottles
Two; polyethylene or
glass; 500 ml
Visually check for
damage upon receipt
As above
Storage con-
  tainer
Polyethylene or glass;
500 or 1000 ml
Visually check for
damage upon receipt
As above
Petri dishes
Glass or polyethylene;
sized to fit the glass
fiber filters
Visually check for
damage upon receipt
As above
Graduated
  cylinder
Glass and class A;
250 ml with subdivi-
sions <2 ml
Upon receipt, check
for stock number,
cracks, breaks, and
manufacturer flaws
As above
Balance
Capable of measuring
silica gel to ±0.5 g
Check with standard
weights upon receipt
and before each use
Replace or
return to
manufacturer
Funnel
Glass suitable for use
with sample bottles
Visually check for
damage upon receipt
Replace or
return to
supplier
Rubber police-
  man
Properly sized
Visually check for
damage upon receipt
As above
Analytical
Equipment

Beakers and
  weighing
  dishes
Glass
Upon receipt, check
for stock number,
cracks, breaks,  and
manufacturing flaws
Replace or
return to
manufacturer
(continued)

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                                                      Section No. 3.11.1
                                                      Revision  No.  0
                                                      Date January  4,  1982
                                                      Page 8 of 9
                                                                 o
Table 1.1 (continued)
Apparatus'
Triple beam
  balance
Analytical
  balance
Filters
Temperature
  gauge
Hygrometer
Reagents

Silica gel
Distilled water
 Stopcock grease
Acceptance limits
500-g capacity; cap-
able of measuring with-
in ±1 g
Capable of measuring to
±0.1 mg
Glass fiber without
organic binder; 99.95%
collection efficiency
for 0.3 u dioctyl
phthalate smoke
particles
Proper operating con-
dition
Proper operating con-
dition
Indicating type 6-16
mesh
Meets ASTM D1193-74;
type 3  (only when
impinger particulate
catch included)
 Acetone  insoluble, heat
 stable silicone grease
Frequency and method
   of measurements
Check with standard
weights upon receipt
and before each use
Check with standard
weights upon receipt
and before each use
Manufacturer's guar-
antee that filters
were tested according
to ASTM D2986-71; ob-
serve under light
for defects
Visual inspection for
damage; compare with
a mercury-in-glass
at room temperature
Visual inspection for
damage; compare with
another instrument
Upon receipt, check
label for grade or
certification
Check each lot, or
specify type when or-
dering
 Upon receipt, check
 label for grade or
 certification
Action if
requirements
are not met
Replace or
return to
manufacturer
As above
Return to
supplier
As above
As above
As above
 Replace or
 return to
 manufacturer
As above
 (continued)
O
                                                                                   O

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                                                     Section No.  3.11.1
                                                     Revision No.  0
                                                     Date  January 4, 1982
                                                     Page  9 of  9
Table 1.1 (continued)
Apparatus
Acceptance  limits
Frequency  and method
   of measurements
Action if
requirements
are not met
Acetone
ACS grade;  <0.001%
residue in  glass
bottles
Upon receipt,  verify
residue by  evaporat-
ing a blank sample
Replace or
return to
plier
Desiccant
Indicating type  anhy-
drous calcium sulfate
Upon receipt,  check
for grade and  certi-
fication
As above

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o
o
o

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                                             Section No. 3.11.2
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 1 of 2
2.0  CALIBRATION OF APPARATUS
     Calibration of apparatus is one of the most important func-
tions  in maintaining  data  quality.   The  detailed calibration
procedures included in  this  section are designed for the equip-
ment specified  by Method 17  as described  in  the previous sec-
tion.  A  laboratory log book of all  calibrations  must be main-
tained.  Table  -2.1 summarizes  the  quality assurance activities
for calibration.   This  section  is  the same as Method 5 (Section
3.4.2).

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                                                     Section No.  3.11.2
                                                     Revision No. 0
                                                     Date January 4,  1982
                                                     Page 2 of  2
                                                               o
         TABLE 2.1.   ACTIVITY  MATRIX FOR CALIBRATION OF EQUIPMENT
Apparatus
Wet test meter
Dry gas meter
Thermometers
Barometer
Probe nozzle
Analytical
  balance
Acceptance limits
Capacity >3.4 mVh
(120 ftVh); accuracy
within
Y1 = Y +0.02 Y
Impinger thermometer
+1°C (2°F); dry gas
meter thermometer
+3°C (5.4°F) over
range; stack tempera-
ture sensor ±1.5% of
absolute temperature
+2.5 mm (0.1 in.) Hg of
mercury-in-glass barom-
eter
Average of three ID
measurements of nozzle;
difference between high
and low <0.1 mm
(0.004 in.)
±1 mg of Class-S
weights
Frequency and method
    of measurement
Calibrate initially,
and then yearly
by liquid dis-
placement (Sec
3.4.2)
Calibrate vs wet
test meter initially,
and when posttest
check exceeds
Y +0.05 Y
Calibrate each ini-
tially as a separate
component against a
mercury-in-glass
thermometer; then
before each field
trip compare each as
part of the train
with the mercury-in-
glass thermometer
Calibrate initially
vs mercury-in-glass
barometer; check
before and after
each field test
Use a micrometer to
measure to near-
est 0.025 mm (0.001
in.)
Check with Class-S
weights upon receipt
Action if
requirements
are not met
Adjust until
specifica-
tions are
met, or re-
turn to
manufacturer
Repair, or
replace and
then recali-
brate
Adjust; de-
termine a
constant
correction
factor; or
reject
Adjust to
agree with a
certified
barometer
Recalibrate,
reshape, and
sharpen when
nozzle be-
comes nick-
ed, dented,
or corroded
Adjust or
repair
O
                                                                                 o

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                                             Section No.  3.11.3
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 1 of 3
3.0  PRESAMPLING OPERATIONS  .
     The quality assurance activities for presampling operations.
are  summarized  in Table  3.1 at the  end of this  section.   See
Section 3.0,  of this Handbook  for details on  preliminary  site
visits.  This section is the  same as Method  5 (Section 3.4.3)
with the exception of the filter holder as detailed below.
     A pretest  check will have  to be made on  most of the  sam-
pling  apparatus.   Figure 3.2 shown in Section  3.4.3 (Method 5)
or a similar  form  is recommended to aid the tester in preparing
an  equipment  checklist,  status  form,   and  packing  list  for
Methods 1 through 8,  Method 17, and particle sizing.
     Filter holders  should be washed with  tap  water,  then  with
deionized  distilled  water and  rinsed with acetone.   Allow the.
filter holder to air dry.   The filter holder  should  have  been
checked for proper design to remain leakless at the temperature
for  which sampling  is  to  be  performed.   Inspect the  filter
holder  gasket  and  replace  if  necessary.   The proper  gasket
material must be used for the stack temperature expected (i.e.,
a Teflon gasket will not work at 500°F).  It is usually best to
pack all types  of  gasket material normally used for that filter
holder in  the event that the stack temperature is  not the  same
as reported in the pretest preparation.  The manufacturer's sug-
gested temperature range should be known for each type of gasket
material used.

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                                                      Section No.  3.11.3
                                                      Revision No. 0
                                                      Date  January 4,  1982
                                                      Page  2 of  3
                                                                o
             TABLE 3.1   ACTIVITY MATRIX FOR PRESAMPLING OPERATIONS
Apparatus
Probe
Impingers,
  filter
  holders, and
  glass con-
  tainers
Pump
Dry gas meter
Reagents and
  Equipment

Sampling fil-
  ters
Acceptance limits
1.  Probe extension free
of contaminants
                 2.   Probe leak free
                 at 380 mm (15  in.) Hg
Clean and free of
breaks, cracks, leaks,
etc.
Sampling rate of 0.02-
0.03 nrvmin (0.66 to
1.0 ftVmin) up to 380
mm (15 in.) Hg at pump
inlet
Clean and readings
within ±2% of average
calibration factor
Free of irregularities,
flaws, pinhole leaks;
desiccate 24 h at 20°
±5.6°C (68° ± 10°F),
or oven dry at 105°C
(220°F) 2 to 3 h;
constant weight ±0.1 mg
Frequency and method
   of measurements
1.  Clean probe in-
ternally by brushing
with tap water, de-
ionized distilled wa-
ter, and acetone; air
dry before test
                         2.   Visually  check be-
                         fore test
Clean with detergent,
tap water, and
deionized distilled
water
Service every 3 mo
or upon erratic be-
havior; check
oiler jars every 10
tests
Calibrate according
to Sec 3.4.2; check
for excess oil
Visually check prior
to testing; weigh on
balance to 0.1 mg
prior to field use
Action if
requirements
are not met
1.   Repeat
cleaning and
assembly pro-
cedures
                       2.   Replace
Repair or
discard
                 O
Repair or re-
turn to manu-
facturer
As above
Replace
 (continued)
                                                                                  O
                                                                   •Jt<>

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                                                      Section No. 3.11.3
                                                      Revision  No. 0
                                                      Date January 4,  1982
                                                      Page 3 of 3
Table 3.1 (continued)
Apparatus
Water
Stopcock grease
Sample recovery
  acetone
Packing Equip-
  ment for
  Shipment

Impingers, con-
  tainers, and
  assorted
  glassware
Pump
Meter box
Wash bottles
  and storage
  containers
Acceptance limits
Deionized distilled
conforming to
ASTM-D1193-74, Type 3
Acetone insoluble,
heat stable silicone
grease
Reagent grade, <0.001%
residue in glas?
bottles
Rigid container pro-
tected by polyeth-
ylene foam
Sturdy case lined with
polyethylene foam ma-
terial if not part of
meter box
Meter box case and/or
additional material  to
protect train compon-
ents; pack spare meter
box
Rigid foam-lined con-
tainer
Frequency and method
   of measurements
Run blank evapora-
tions prior to field
use to eliminate high
solids (only required
if impinger contents
to be analyzed)
Check label  data upon
receipt
Run blank evapora-
tions upon receipt
Prior to each ship-
ment
As above
As above
As above
Action if
requirements
are not met
Redistill  or
replace
Replace
Replace or
return to
supplier
Repack
As above
As above
As above
                                                                    7

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o
o
o

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                                             Section No. 3.11.4
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 1 of 6
4.0  ON-SITE MEASUREMENTS
     The  on -site  activities  include transporting  equipment to
the  test  site, unpacking  and assembling the  equipment,  making
duct measurements, performing the velocity traverse, determining
molecular weights  and  stack gas moisture contents,  sampling for
particulates,  and recording the data.  Table 4.1 at  the  end of
this  section  summarizes  the  quality assurance  activities  for
on -site  activities.   Blank  data  forms  are  in Section 3.4.12
(Method 5)  for the convenience of the Handbook user.   This sec-
tion is the same  as Method 5 (Section 3.4.4) with the exception
of the items detailed below.
4.1  SAMPLING
4.1.1   Sampling Train Preparation  -  During  preparation  of  the
sampling  train, keep  all  openings where contamination can occur
covered  until  just prior  to assembly  or  until sampling com-
mences.
     Place  100 ml of distilled water (a graduated  cylinder may
be used)  in each of the first two impingers; leave the third im-
pinger  empty;  and place £200-300 g of  preweighed silica  gel in
the  fourth  impinger.   Record the  weight of the silica gel and
the  container on  the  appropriate  data form.    Place  the empty
container in  a safe place for use later in the sample recovery.
If moisture content is to  be determined by  impinger analysis,
weigh  each  of the  first  three impingers to  the nearest 0.5 g,
and record  these weights.
     Using  a  tweezer  or clean disposable surgical gloves, place
a  filter in  the  filter  holder.   Be sure  that the  filter is
properly  centered  and  that  the  gasket  is  properly  placed to
prevent  the sample  gas stream  from  circumventing the filter.
Note:   Some filter  holder designs require  the use  of a glass
fiber  thimble.  If this  type of filter  is  used, ensure  that a
good fit  is made.  Poor quality control in filter production by

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                                             Section No.  3.11.4
                                             Revision No.  0
                                             Date January 4,  1982
                                             Page 2 of 6
o
some manufacturers  have  resulted in a loose fit  or  the  tearing
of the filter from too tight of a fit.4
4.1.2  Sampling Train Assemblage  -  Assemble  the train as  shown
in Figure 1.1, using (if necessary) a very  light  coat of  sili-
cone grease  only  on the  outside of all  ground-glass  joints to
avoid contamination.   Place  crushed  ice  and  water around  the
impingers.
     If not  already an integral  part  of  the  probe  assembly,  a
temperature sensor should be attached to the metal sheath of the
sampling probe so that the sensor  extends beyond the  probe tip
and does not  touch  any metal.  Its position should be about 1.9
to 2.54 cm (0.75  to 1 in.) from the pitot tube and the nozzle to
avoid interference  with  the  gas flow.   Alternative arrangements
are shown in Method 2.  Note;  Because of the larger diameter of
the  in-stack filter  holders,  it  is  critical  that the  3  in.        [)
minimum spacing be  observed from the  nozzle tip to  the  closest
portion of the filter holder.
4.1.3  Sampling Train Leak Checks - Leak checks are necessary to
assure that  the sample has not been biased  low by dilution  air.
The  Reference  Method  (Section  3.11.10)  specifies that  leak
checks be performed at certain times as discussed below.
     Pretest  - A  pretest leak check is recommended, but not re-
quired.  If  the  tester opts  to  conduct the  pretest leak  check,
the following procedure should be used:
     After  the  sampling  train  has  been  assembled,  plug  the
nozzle with a material that can withstand  the  stack  temperature.
Place the filter holder in the stack and allow time  for the  fil-
ter  temperature  to stabilize  with  the stack temperature.    Leak
check  the  train by pulling  a 380 mm  (15 in.)  Hg vacuum.  Note;
A  lower vacuum may be  used  if  it is not  exceeded during the
test.  Also after the  filter  holder has been heated  to the stack        /*~"N
temperature,  it may be necessary  to remove it  from the stack and        ^—^
retighten before  it will  pass  the leak check.

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                                             Section No.  3.11.4
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 3 of 6
     Posttest - Same as for Method 5.
4.1.4   Sampling Train Operation  - Just  prior to placing  probe
in-stack to heat  filter  holder,  clean the portholes to minimize
the chance of sampling deposited material.  Place the capped off
filter  holder  in the  stack and  allow sufficient time  for the
filter  holder  to  equilibrate with the stack temperature.   This
may take as much as 30 min for some stacks.
4.2  SAMPLE RECOVERY
     The Reference  Method  (Section  3.11.10) requires  that the
sample  be  recovered  from  the  nozzle and  all  sample  exposed
portion of the filter holder and the filter in an area sheltered
from wind and dust to prevent contamination of the sample.    The
capped-off  impinger box  or condenser  system  and the  capped
sampling probe  can  be transported  to the cleanup  area without
risk of losing or contaminating the sample.
4.2.1   Filter  - Initially  take  three unused filters  for  each
field test series and label them as filter blanks.   (These three
should have been tared when the sample filters were tared,  since
they are used  as  the  control samples  for  the check on. the ana-
lytical balance.)  The filter used for the sample run should be
recovered.   Using a pair  of tweezers and/or clean  disposable
surgical  type  gloves,   carefully remove  the  filter  from the
filter  holder,  and  place it in its  designated petri  dish.   Any
filter  fibers or  particulates which adhere to the filter gasket
should  be  removed with  a  nylon  bristle brush or  a sharp  blade
and  placed  in the  container,  which should  then be  closed,
sealed, and  labeled.   Note:  When  the filter holder  is opened
check the  filter  for  tares in the collection area and check the
sealed  area  to determine  if any particulate has  bypassed the
seal  or  if the  filter was improperly  placed  in the  filter
holder.
4.2.2   Nozzle  and Filter Holder  -  Initially,  put  a  minimum of
200 ml  of the  acetone  used  for sample  recovery in a sample

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                                             Section No. 3.11.4
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 4 of 6

bottle, mark the liquid level, seal, and label the bottle.  Then
enter  the  bottle  number  on  the  sample recovery  and integrity
form.  A  single sample bottle is usually  adequate  for the col-
lection of all  the rinses;  it should be labeled and recorded in
the same manner as the blank sample.
     Clean the  outside of the probe  filter  holder,  pitot tube,
and  nozzle  to prevent particulates from being brushed into the
sample bottle.  Carefully remove the probe nozzle, and rinse the
inside surface  (using  a  nylon bristle brush and several acetone
rinses) into the sample bottle until no particles are visible in
the  rinse.   Then  make one final rinse  of the nozzle  with the
acetone.   Clean the   swagelok  fitting by the  same procedure.
After  rinsing each  component,  rinse  the  sample off the brush
into the sample container.
     Distilled  water may  be  used  instead of  acetone  when ap-
proved by the administrator and should be used when specified by
the  administrator.   In  these  cases, save  a  water blank  and
follow administrator's directions on  analysis.
     After ensuring  that  all  joints are wiped clean  of silicone
grease  (if  applicable),  clean  the  inside  of  the  front half
(sample  exposed portion)  of  the  filter holder  by  rubbing the
surface  with the  brush and  rinsing  with acetone.   Rinse each
surface three  times  or more if needed to remove visible partic-
ulate.  Make final rinse of the brush and filter holder.
     After all the rinsings have been collected, tighten the lid
on  the  sample bottle  securely.    As a precaution  in  case of
leakage,  mark the acetone  level  on  the bottle,  and note it on
the  sample recovery  form  (Figure 4.4  of Method  5).
                                                         cA
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                                                      Section No. 3.11.4
                                                      Revision  No. 0
                                                      Date January 4,  1982
                                                      Page 5 of 6
            TABLE 4.1.   ACTIVITY MATRIX  FOR ON-SITE MEASUREMENT CHECKS
Apparatus
Sampling

Filter
Condenser
  (addition of
  reagents)
Assembling
  sampling
  train
Sampling
  (isokineti-
  cally)
(continued)
Acceptance limits
Centered in holder;  no
breaks, damage,  or con-
tamination during load-
ing
100 ml of distilled
water in first two
impingers; 200-300 g of
silica gel in fourth
impinger
1.  Assembly specifica-
tions in Fig 1.1
                 2.   Leak rate <4% or
                 0.00057 mVmin (0.02
                 ftVmin),  whichever is
                 less
1.  Within ±10% of
isokinetic condition
                 2.   Standard checked
                 for minimum sampling
                 time and volume;  sam-
                 pling time/point  >2 min
                 3.   Minimum number of
                 points specified by
                 Method 1
Frequency and method
   of measurements
Use tweezers or surg-
ical gloves to load
Use graduated cylinder
to add water, or weigh
each impinger and its
contents to the near-
est 0.5 g
1.  Before each sam-
pling run
                         2.   Leak-check before
                         sampling by plugging
                         the nozzle or inlet
                         to first impinger and
                         by pulling a vacuum of
                         380 mm (15 in.) Hg
1.  Calculate for
each sample run
                         2.   Make a quick cal-
                         culation before test,
                         and exact calculation
                         after
                         3.   Check before the
                         first test run by mea-
                         suring duct and using
                         Method 1
Action if
requirements
are not met
Discard fil-
ter, and re-
load
Reassemble
system
1.
ble
Reassem-
                       2.   Correct
                       the leak
1.   Repeat
the test run
                           As above
                       3.   Repeat
                       the procedure
                       to comply
                       with specifi-
                       cations of
                       Method 1

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                                                      Section No.  3.11.4
                                                      Revision  No. 0
                                                      Date  January 4,  1982
                                                      Page  6 of 6
                                                                    o
Table 4.1 (continued)
Apparatus
Sample recover}/
Sample
  logistics,
  data collec-
  tion, and
  packing of
  equipment
Acceptance limits
                 4.   Leakage  rate
                 <0.00057  mVmin (0.02
                 ft3/min)  or  4% of  the
                 average sampling vol-
                 ume,  whichever is  less
Noncontaminated sample
1.   All  data recorded
correctly
                 2.   All  equipment  exam-
                 ined for damage  and
                 labeled  for shipment
                 3.   All  sample  contain-
                 ers and  blanks  properly
                 labeled  and packaged
Frequency and method
   of measurements
                         4.   Leak check  after
                         each test run or  be-
                         fore equipment  re-
                         placement during  test
                         at  the  maximum  vacuum
                         during  the test (man-
                         datory)
Transfer sample .to
labeled polyethylene
containers after
each test run;  mark
level of solution in
the container
1.   After completion
of each test and be-
fore packing
                         2.   As .above
                         3.   Visually check
                         upon completion of
                         each sampling
Action if
requirements
are not met
                       4.   Correct
                       the  sample
                       volume,  or
                       repeat  the
                       sampling
Repeat the
sampling
1.  Complete
data
O
                       2.   Repeat
                       the sampling
                       if  damage oc-
                       curred during
                       the test
                       3.   Correct
                       when possible
                                                                                      O

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                                                    Section No.  3.11.5
                                                    Revision No. 0
                                                    Date January 4,  1982
                                                    Page 1 of  1
 5.0  POSTSAMPLING OPERATIONS

      Table  5.1  summarizes  the  quality assurance  activities  for

 the postsampling operations.  This  section is  the same  as Method

 5 (Section 3.4.5).
           TABLE 5.1.  ACTIVITY MATRIX FOR POSTSAMPLING  OPERATIONS
Apparatus
Sampling

Dry gas  meter
Meter thermome-
  ter
Barometer
Stack tempera-
  ture
Acceptance  limits
Within ±5% of calibra-
tion factor
Within ±6°C  (10.8°F)
at ambient pressure
Within ±5  mm  (0.2 in.)
Hg at ambient pressure
Within ±1.5%  of the
reference  check temp-
erature (°R)
Frequency  and method
   of measurements
Make three  runs at a
single,  intermediate
orifice  setting and
at highest  vacuum
occurring during test
(Sec 3.4.2)
Compare with ASTM
mercury-in-glass
thermometer after
each field test
Compare with  mercury-
in-glass barometer
after each  field
test
After each  run, com-
pare with reference
temperature
Action if
requirements
are not met
Recalibrate
and use cali-
bration fac-
tor that
gives lesser
sample volume
Recalibrate
and use
higher tem-
perature for
calculations
Recalibrate
and use lower
barometric
values for
calculations
Recalibrate
and calculate
with and
without tem-
perature cor-
rection
                                                             A/ 2

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                                                 Section No.  3.11.6
                                                 Revision No.  0
                                                 Date January 4, 1982
                                                 Page 1 of  1
 6.0  CALCULATIONS

      Calculation errors due to  mathematical  mistakes  can  be a

 large part of  total system  error.  Therefore,  each set  of calcu-

 lations  should  be  repeated  or  spot checked by a  team  member

 other than  the one  who performed them  originally.   If  a differ-

 ence  greater  than  a  typical  roundoff error  is  detected,  the

 calculations should be checked  step by  step until the  source of

 error is  found and  corrected.   A computer program can  be advan-

 tageous  in  reducing  calculation  errors.   If   a   standardized

 computer  program is  used,  the  original  data  entry  should be

 checked; if  differences are observed,  a new computer run should

 be made.  Table 6.1  summarizes  the quality assurance activities

 for calculations.  This section is the  same as Method 5 (Section

 3.4.6).
                TABLE 6.1.  ACTIVITY MATRIX FOR CALCULATIONS
Apparatus
Acceptance limits
Frequency and  method
   of measurements
Action if
requirements
are mot met
Analysis data
  form
All  data and calcula-
tions given on the
form
Visual check
Complete the
missing data
values
Calculations
Difference between
checked and original
calculations not in
excess of roundoff
error; at least one
decimal figure beyond
that of acquired data
retained
Repeat all calcula-
tions starting with
raw data for hand
calculations and for
one sample per test
Indicate er-
rors  in ana-
lysis; data
on Fig 6.1A
or B  (Sec
3.4.6)
Isokinetic
  variation
90% <  I < 110%;  see
Eqs 6.9 and 6.10 (Sec
3.4.6) calculation
of I
For each run,  calcu-
late I
Repeat the
test, and ad-
just flow
rates to
maintain I
within ±10%
variation

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                                             Section No. 3.11.7
                                             Revision No. 0
                                             Date -January 4, 1982
                                             Page 1 of 2
7.0 MAINTENANCE
     Normal  use  of  emission  testing  equipment subjects  it  to
corrosive gases,  temperature  extremes, vibrations,  and shocks.
Keeping the  equipment in good operating  order over an extended
period of time requires routine maintenance and knowledge of the
equipment.  Maintenance  of the entire  sampling train should be
performed  either  quarterly  or   after 1000  ft3  of  operation,
whichever occurs  sooner.  Maintenance  procedures are summarized
in  Table  7.1.   These  procedures  are  recommended,  but  not re-
quired,  to  increase  the   reliabilty  of  the  equipment.   This
section is the  same as Method 5  (Section 3.4.7)  except for the
following addition.
     Because of  their design and  use,  many  filter  holders are
high maintenance  items.  The  filter holder must be cleaned, the
bent and  damaged parts  replaced,  the  filter surfaces smoothed,
and the  gaskets  cleaned or replaced to  ensure that the filter
holder remains  leak tight, does not contaminate the sample and
does not tear the filter.

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                                                     Section No.  3.11.7
                                                     Revision No.  0
                                                     Date January 4, 1982
                                                     Page 2  of 2
                                                                  o
          TABLE 7.1  ACTIVITY MATRIX  FOR EQUIPMENT MAINTENANCE CHECKS
Apparatus
Routine main-
  tenance
Fiber vane pump
Diaphragm pump
Dry gas meter
Inclined manom-
  eter
Sample train
Nozzle
Acceptance limits
No erratic behavior
Lea(<; free; required
flow
Leak-free valves func-
tioning properly; re-
quired flow
No excess oil,  corro-
sion, or erratic dial
rotation
No discoloration of or
visible matter in the
fluid
No damage or leaks
 No  dents, corrosion,
 or  other damage
Frequency and method
   of measurements
Routine maintenance
quarterly; disassem-
ble and clean yearly
Periodic check of oil
jar; remove head and
change fiber vanes
Clean valves during
yearly disassembly
Check every 3 mo for
excess oil or corro-
sion by removing the
top plate; check
valves and diaphragm
when meter dial runs
erratically or when
meter will not cali-
brate
Check periodically;
change fluid during
yearly disassembly
Visually check every
3 mo; completely
disassemble and clean
or replace yearly
Visually check be-
fore and after each
test run
Action if
requirements
are not met
Replace parts
as needed
Replace as
needed
Replace when
leaking or
when running
erratically
Replace parts
as needed, or
replace meter
Replace parts
as needed
If failure
noted, use
another en-
tire control
console, sam
ple box, or
umbilical
cord
Use  another
nozzle or
clean,
sharpen, and
recalibrate
O
o
                                                                                   J1-

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                                             Section No. 3.11.6
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 1 of 2
8.0  AUDITING PROCEDURE
     An  audit is  an  independent assessment  of data  quality.
Independence  is  achieved by using apparatus  and standards that
are different from those used by the regular  field crew.   Rou-
tine quality  assurance  checks  by a field team are necessary for
obtaining good  quality data, but  they  are not  part of the au-
diting procedure.   Table 8.1  summarizes  the  quality assurance
activities for the auditing.  This section is the same as Method
5  (Section  3.4.8) with the exception  of the system audit de-
scription.
     The  major  difference  in  the system  audit of Method  17
versus Method 5  is that the in-stack filter holder is heated by
the stack.  This  temperature is critical 1) before test for the
pretest  leak  check,  2) during  sample extraction, and 3) during
the posttest  leak check.   The observer  should be satisfied that
the filter holder temperature  is relatively close to the actual
stack temperature.

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                                                     Section No. 3.11.8
                                                     Revision  No. 0
                                                     Date January 4,  1982
                                                     Page 2 of 2
                                                                 o
             TABLE 8.1.   ACTIVITY  MATRIX  FOR AUDITING PROCEDURES
Audit
Volumetric
  sampling
  phase of
  Method 17
Data processing
  errors
Systems audit
Acceptance limits
Measured pretest volume
within ±10% of the
audit volume
Original and check caV
culations agree
Conducted method as
described in this sec-
tion of the Handbook
Frequency and method
   of measurement
Once during every en-
forcement source
test, measure ref-
erence volume,  and
compare with true
volume
Once during each
enforcement source
test, perform inde-
pendent calculations
starting with the
recorded data
Once during each
enforcement test
until experience
gained, then every
fourth test, observe
techniques; use
audit checklist
Fig 8.1 (Sec 3.4.8)
Action if
requirements
are not met
Review oper-
ating tech-
nique
Check and
correct all
data
Explain to
team the de-
viations
from recom-
mended tech-
niques; note
the devia-
tions on Fig
8.1 (Sec
3.4.8)
O
                                                                                  O

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                                             Section No. 3.11.9
                                             Revision No. 0
                                             Date January 4,  1982
                                             Page 1 of 1
9.0  RECOMMENDED STANDARDS FOR ESTABLISHING TRACEABILITY
     To achieve data  of  desired quality,  two considerations are
necessary:   (1) the measurement process  must be in  a state of
statistical  control,  and  (2)  the  systematic errors,  when com-
bined with  the random variations  (errors  of measurement), must
result in a suitably small uncertainty.
     To ensure good  data,  it  is  necessary  to  perform quality
control checks and independent audits of the  measurement pro-
cess; to  document  the data by quality control charts  (as appro-
priate); and to use materials, instruments, and procedures which
can be traced to a standard of reference.
     The  working  calibration  standards  should  be  traceable to
primary or  higher  level  standards  such  as  those  listed below.

     1.   The  dry  gas meter should be calibrated  against a wet
          test meter which has been verified by liquid displace-
          ment, as described in Section 3.4.2.

     2.   The  analytical  balance  should  be  checked  against
          Class-S  weights  that are traceable to NBS standards.

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                                                                          Section  No.  3.11.10
                                                                          Revision No.  0
                                                                          Date  January  4,  1982
                                                                          Page  1  of  11
10.0    REFERENCE  METHOD*
  Taken  from
  February  237
Federal
   txcrxoo  it. BrnnuiKATion  or
     •MISSIONS raoM RATIONAXT souitczs (IN-
     STACK ftLTTUTIOH HTTROD)

                 Introduction
     PartlCjulate  matter  is  not an  absolute
   quantltyr.rather, it is a function of tempera-
   ture and1 pressure.  Therefore, to prevent
   variability  In paniculate matter  emission
   regulations and/or associated test methods,
   the temperature and pressure at which par-
   ticulate  matter is to be measured must be
   carefully defined. Of the two variables (I.e..
   temperature and pressure), temperature has
   the greater effect upon the  amount of par-
   ticulate matter in an effluent eat stream: in
   most stationary source categories, the effect
   of pressure appears to be negligible.
     In method 8. 250* P is established as a
   nominal  reference   temperature.  Thus,
   where Method 5 Is specified  in an applicable
   subpart of the standards, paniculate matter
   is defined  with respect to temperature. In
   order to maintain a collection temperature
   of 250* F. Method 5 employs a heated (lass
   cample probe and a  heated filter holder.
   This equipment is somewhat cumbersome
   and requires care In  its operation. There-
   fore, where  paniculate matter concentra-
   tions (over the normal rante of temperature
   associated with a specified source category)
   are  known to be independent of tempera-
   ture, it  Is  desirable to eliminate  the glass
   probe and  heating systems, and sample at
   stack temperature.
     This method describes an la-stack sam-
   pling  system and sampling  procedures for
   use in such cases. It Is intended to be used
   only when specified by an  applicable  sub-
   part of the standards, and only within the
   applicable temperature limits (if specified).
   or when otherwise approved by the Admin-
   istrator.
     1. Principle and Applicability.
     1.1  Principle. Paniculate  matter Is with-
   drawn isokinetically  from the source and
   collected on  a glass fiber filter maintained
   at stack temperature.  The paniculate macs
   Is determined gravtmetrically after removal
   of uncomblned water.
     1.2  Applicability. This method applies to
   the  determination of paniculate emissions
   from  stationary sources for determining
   compliance with new source performance
   standards,  only when  specifically provided
   for  in an applicable subpart of the  stan-
   dards. This  method is not applicable to
   stacks that contain liquid droplets or are
   saturated with water vapor. In addition, this
   method shall not be used as written if the
   projected cross-sectional area of the probe
   extension-filter  holder  assembly  covers
   more than S  percent of the  stack cross-sec-
   tional area (see Section 4.1.2).

     2. Apparatus.
     2.1  Sampling Train. A schematic  of the
   sampling train used in this method is shown
   in  Figure  17-1.  Construction details  for
   many, but not  all. of  the train components
   are given In  AFTD-OS81 (Citation 2 in Sec-
   tion 7); for  changes from  the APTD-OS81
   document  and for allowable modifications
   to Figure 17-1. consult with  the Administra-
   tor.
Register,   Vol.  43,  No.  37
    1978.
Thursday,

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            TEMPERATURE     IflSTACK
                          FILTER HOLDER
 . r > 1.9 en O.TS ta->*    \ J
              '
O
                                                                                                 MAY or REPLACED
                                                                                 av An tauiVAiCMT corioEfcSER
                                                                                                                     TIIERtJC3ETin


                                                                                                                         . CHECK
                                                                                                                       / VALVE
                         REVEttSE-TYPE
                          PITOT TUOE
                                ORIFICE MAn SUGGESTED (INTERFERENCE FREE) SPACtflGS
                                       Fhura 17-1. PcrtteulalfrSsmplingTrdn. Equtppsd wUh fn-Slech Fitter.
o
                                                                                                                               VO
                                                                                                                               CO
                                                                                                                               ro
o

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                                                                                     Section  No.  3.11.10
                                                                                     Revision  No.  0
                                                                                     Date  January  4,  1982
                                                                                     Page  3  of  11
  The operating  and maintenance proce-
 dures (or many of the sampling train  com-
 ponents  are described In APTD-0576 (Cita-
 tion  3 in Section  7).  Since correct  usace is
 Important in  obtaining  valid results, all
 users should read the AFTD-0976 document
 tad adopt the opentint  and maintenance
 procedure* outlined in it, unless otherwise
 specified herein. The sampling train  con-
 lists of the following components:
  3.1.1  Probe  Nozzle. Stainless steel  (316)
 or  dais, with  sharp, tapered leading edge.
 The  angle of taper shall be 030*  and the
 taper shall be  on  th« outside to preserve a
 constant  internal diameter.  The probe
 node shall be of  the button-hook or elbow
 design, unless otherwise specified by the Ad-
 ministrator. If made  of stainless steel, the
 nozxle shall be constructed  from taintless
 tubing. Other materials of construction mar
 b»  used  subject to the approval of the Ad-
 ministrator.
  A rang* of  sisss  suitable for Isotclnetlc
'campling should be available, e.g., 0.32 to
 1.27  cm  (H to H in)—or larger if higher
 volume sampling trains are  used—inside di-
 uaeter (ID) nozzles in Increments of 0.18 cm
 (Vii in).  Each nozzle  shall be calibrated ac-
 cording to the procedures outlined in Sec-
 tion S.I.
  2.1.2 Filter  Bolder. The  In-tUck filter
 bolder shall be constructed  of borosllicate
 or quartz glass, or stainless steel: U  a gasket
 Is used. It shall be made of  sUicone rubber.
 Teflon, or stainless steel. Other holder and
 gasket materials may be used subject to the
 approval  of the Administrator. The fDter
 bolder shall be designed to  provide a  posi-
 tive teal  against leakage from the outside or
 around the filter.
  2.1.3 Probe Extension. Any suitable  rigid
 probe extension may be used after the filter
 holder.
  2.1.4 Pilot Tube. Type 8. as described In
 {Section 2.1 of Method 2. or other device ap-
 proved by the Administrator the pilot tube
 shall be  attached to the probe extension to
 allow constant monitoring of the stack gu
 velocity (te* Figure 17-1). The impact (high
 pressure) opening plane of the pltot  tub*
 thall be even with or above the ooslc entry
 plane during  sampling  (tee Method X
 Figure 2-«b).  It is recommended:  (1)  that
 the pilot tube have a known baseline coeffi-
 cient, determined as outlined in Section 4 of
 Method  2: and (2) that this known coeffi-
 cient be  preserved by placing the pltot tube
 In an interference-free arrangement with re-
 spect to  the sampling node, filter holder,
 and temperature sensor (see Figure  17-1).
 Note that the 1.9 cm  (0.75 in) free-space be-
 tween the nozzle  and pltot tube shown in
 Figure 17-1. U  based on a U cm (0.5 in) ID
 nozzle. If the sampling train is designed for
 sampling at hither flow rates than that de-
 scribed in AFTD-0581. thus necessitating
 the use  of  larger sized  nozzles, the  free-
 space shall be 1.9 cm (0.76 in) with the larg-
 est sited  nozzle In place.
  Source-sampling assemblies that do not
 meet the minimum spacing requirements of
 Figure 17-1 (or the equivalent of these re-
 quirements, e.g.. Figure  2-7 of Method 2)
 may be uted; however, the pltot tube coeffi-
 cients of such assemblies  thall  be deter-
 mined by calibration, using methods subject
 to the approval of  the Administrator.
  2.1.8 Differential   Pressure  Oauge. In-
 clined manometer  or   equivalent device
 (two), as described In Section 2.2 of Method
 2. One manometer shall be used for velocity
 b«ttd (Ap) readings, and  the other, for ori-
 lisa differential pressure reafllnss.
  2.1.6 Condenser. It is recommended that
the iznplnger system described In Method 5
be used to determine the moisture content
of the stack  gu. Alternatively, any system
that allows measurement of both the  water
condensed and the moisture leaving the con-
denser, each  to within I  ml or 1 g, may be
used. The  moisture  leaving the condenser
can be measured either by: (1) monitoring
the temperature and pressure at the exit of
the  condenser  and  using Dillon's  law of
partial pressure*: or  (2) passing the sample
gas stream through  a silica gel trap with
exit  gue* kept below 20* C (68' F> and  de-
termining the weight rain.
  Flexible tubing may be used between the
probe  extension  and condenser. If means
other than silica gel are used  to determine
the  amount  of  moisture leaving the con-
tfsnsar, It is recommended that silica gel still
be ustd between the condenser system tad
pump to prevent moisture condensation in
the pump and metering devices and to avoid
the ne«d to make corrections for moisture
In the metered volume.
  2.1.7 Metering System.  Vacuum gauge.
leak-free pump,  thermometers  capable of
meacuring temperature to within 3* C (S.4*
F).  dry gru  meter  capable of measuring
volume to within 2 percent,  and  related
equipment, as shown in Figure 17-1. Other
metering systems capable of  maintaining
campling rates within 10 percent of Isokine-
tlc and of determining sample volumes to
within 2 percent may be used, subject to the
approval of  the  Administrator. When  the
metering system (a used In conjunction with
a pilot tube,  the system shall enable check*
of Isokinctlc rates.
  Campling  trains utilizing  metering sys-
tems  designed for higher flow rates than
that described In APTD-OM1 or APTD-0376
may b* used provided  that the specifica-
tions of this method  are met.
  2.1.8 Barometer.  Mercury,  aneroid, or
other barometer capable of measuring at-
mospheric  pressure  to within 2JS «"«  Eg
(0.1 In. Eg). In many carts, the barometric
reading may  be obtained from a nearby na-
tional weather service station, in which case
the  station  value (which Is  the  absolute
barometric pressure) shall be requested and
an adjustment for elevation differences be-
tween  the weather  station and sampling
point shall be applied at a rate of minus 2.5
mm  Ht (0.1 in. Rg) per 30 m (100 ft)  eleva-
tion increase or  vice versa for elevation de-
crease.
  2.1.9 Gas  Density Determination Equip-
ment.  Temperature  tensor and  pressure
gauge, at described In Sections 2.1 and 2.4 of
Method 2. and eu analyzer. If necessary, as
described in Method  3.
  The temperature tensor thall be attached
to either the pltot tube or to the probe ex-
tension. In a fixed configuration. If the tem-
perature tensor is attached in the field: the
tensor shall  be  placed  In an Interference-
free arrangement with respect to the Type
S pilot tube  openings (ai shown in Figure
17-1 or in Figure 2-7 of Method 2). Alterna-
tively, the  temperature sensor need not be
attached to  either the  probe extension or
pltot tube during sampling, provided that  a
difference of not more than 1 percent  In the
average velocity measurement is Introduced.
This alternative U subject to the approval
of the Administrator.
  2.2 Sample Recovery.
  2.2.1 Probe Nozzle Brush. Nylon  bristle
brush with stainless steel wire handle. The
brush shall be properly sized and shaped to
brush out the probe ncsle.
  2.2.2 Wash -Bottles— Two.  Glass  wttsh
bottles  are  recommended;  polyethylene
wash  bottles may be used at the option of
the tester. It Is recommended that  acetone
not be stored in polyethylene bottles for
longer than a month.
  2.2.3 Glass  Sample  Storage  Containers.
Chemically resistant. boroiUlcate glui bot-
tles. for acetone washes, BOO ml or 1000 ml.
Screw cap liners  thall either be  rubber-
backed Teflon or shall be constructed so as
to be leak-free  and resistant to chemical
attack by acetone. (Narrow mouth glass bot-
tles have  been found  to  be leas prone to
leakage.) Alternatively, polyethylene bottles
may be used.
  2.2.4 Petri  Dishes.  For  filter  samples:
Class  or  polyethylene,  unless  otherwise
cpecified by the Administrator.
  2J.S Graduated  Cylinder  and/or  Bal-
ance.  To measure condensed water to within
1 ml or 1  i. Graduated cylinders shall have
subdivisions no greater than 2 ml. Most lab-
oratory balances are capable of weighing to
the nearest O.S e or less. Any of these bal-
ances is suitable for use here and in Section
2.3.4.
  2.2.6 Plastic  Storage  Containers.  Air
tight  containers to store silica gel.
  2.2.7  Funnel and Rubber Policeman. To
aid in transfer of silica gel to container, not
necessary U'sQIea gel Is weighed in the field.
  2.2.8  Funnel. Glass or polyethylene, to
aid in sample recover}'.
  2.3  Analysis.
  2.3.1  Glass Weighing Dishes.
  2.3.2  Desiccator.
  2.3.3  Analytical Balance. To measure to
within 0.1 mg.
  2.3.4  Balance. To measure to within O.S
mg.                               :  '
  2.3.5  Beakers. 250 ml.
  2.3.6  Hygrometer. To measure the  rela-
tive humidity  of  the laboratory  environ-
ment.
  2.3.7  Temperature  Gauge. To measure
the temperature of the laboratory  environ-
ment.
  3.1  Sampling.
  3.1.1  Filters. The In-stack filters shall be
glass  mats or thimble fiber filters, without
organic binders, and shall exhibit at  least
68.85  percent efficiency (00.05  percent pene-
tration)  on  0.3 micron dioctyl  phthalate
cmoke particles. The filter efficiency  tests
shall  be  conducted  in  accordance  with
ASTM standard  method D 2986-71.  Test
data from the supplier's quality control pro-
gram are sufficient for this purpose.
  3.1.2  Silica Gel. Indicating type. 6- to  16-
mesh. If previously used, dry at 175* C (350*
F) for 2 hours. New silica gel may be used as
received. Alternatively, other types of desic-
canu (equivalent  or better) may be  used.
subject to the approval of the Administra-
tor.
  3.1.3  Crushed Ice.
  3.1.4  Stopcock Grease. Acetone-insoluble.
heat-stable slllcone grease. This is not nec-
essary If  screw-on connectors with Teflon
tleeves. or similar, are used. Alternatively.
other types of stopcock grease may be  used.
subject to the approval of the Administra-
tor.
  3.2  Sample Recovery.  Acetone, reagent
grade. 00.001 percent residue, in glau bot-
tles. Acetone from metal containers general-
ly has a high residue blank and should not
be  used. Sometimes, suppliers transfer  ac-
etone to glaxt bottles from metal container*,
Thus, acetone blanks thai!  be run prior to
field ure and only acetone  with  low blank

-------
values (00.001 percent) shall be used. ID no
emae  shil] a blank value o! crealer than
0.001 percent of the weight of acetone used
b« subtracted frora the cample weight.
  3.3  Analysis.
  3.3.1  Acetone. Same as 3.2.
  3.3.2  Desiccant, .Anhydrous calcium iul-
ftte. Indicating type.  Aliemallvely. other
types of desiccanu may be used, subject to
the approval of the Administrator.
  4. Pmcedure.
  4.1  Samplinc. The  complexity  of this
method is such that, in order to obtain reli-
able results, testers should  be trained and
experienced with the test procedures.
  4.1.1  Pretest  Preparation. All   compo-
nents shall be maintained and calibrated ac-
cordant  to  the  procedure described  In
APTD-057ft,  unless   olhendse  specified
herein.
  Welfh several SCO to  300 i portions of
silica re! in alr-Ughl containers to the near-
est 0.5  g. Record the total  welfht of  the
silica rel plus container,  on each container.
As an alternative, the silica |el need not be
preweighed, but may be weighed dirtclly in
Its impinger or sampling holder lust prior to
train assembly.
   Cheek fillers  Visually against Uiht for Ir-
regularities  and  flaws  or   plnhole leaks.
Label ftlten of the proper tire on  the back
tide near the  edge using  numbering  na-
chine ink. As an alternative, label the ship-
ping container* (class or plastic pctri dishes)
and keep the filters in these containers at
all times except during sampling and weigh-
ing.
   Desiccate the filters at 20=5.6' C (88 = 10'
F) and  ambient  preuure  tor at  least 24
 hours and weigh at Intervals of at least 6
 hours to a constant weight. Le..  00.5 mi
change from previous weighinr. record re-
sults to the  nearest 0.1  rag. During each
weighing the filter oust not be exposed to
 the laboratory  atmosphere for  a period
 greater than 2 minutes  and a relative hu-
midity   above  SO  percent.  Alternatively
 (unless otherwise specified by the  Adminis-
 trator), the fillers may be ov*n dri*d at 105*
 C (220' T1 for 2 to 3 hours, desiccated lor 2
 houn, and weighed. Procedures other than
 those described, which account  for relative
 humidity effects, may be used, subject to
 the approval of the Administrator.
   4.1.2  Preliminary Determinations. Select
 the sampling site and the i-itntmum number
 of sampling points according to Method 1 or
 as specified by the Administrator. Make a
  projecled-area model of the probe exten-
  sion-filter holder assembly, with  the  pilot
  tube face openings positioned along the cen-
  terline of the stack, as shown In Figure 17-2.
  Calculate the estimated cross-section block-
  ace, as shorn In Figure 17-2. If the blockage
  exceeds 5 percent of the duct crocs sectional
  area, the tester  has Ihe following oplions:
  (1) a suluble out-of-slack flllratlon method
  may be used instead of in-slack filtration: or
  (2) t special in-slack arrangement, in which
  the sampling and velocity metsuremeni
  sites are separate, may be used: for details
  concerning this approach,  consult with the
  Administrator (see also Citation  10 In Sec-
  tion 7). Determine the stack preuure. tem-
  perature, and the range  of velocity heads
  using Method 2; it is recommended that a
  leak-check of the pilot  lines (see  Method 2,
  Section  3.1) be  performed. Determine the
  moisture' content  using  Approximation
  Method 4 or its alternatives for the purpose
  of making isokinetlc sampling rate settings.
  Determine the  suck  gas dry  molecular
  weight,  as described in Method  2. Section
  3.6: if Integrated Method 3 sampling Is used
  for molecular weight determination, the In-
  tegrated bag sample shall be taken slmulu-
  oeously with,  and for the same total length
  of Uac'u, the particular tacwlt run.
                                  Section  No.   3.11.10
                                  Revision  No.  0
                                  Date  January  4,  1982
                                  Page  4  of 11
                                                        STACK
                                                        WALL
                                                 o
                                                                            o
 IB-STACK FIITEIV
PflODE EXTENSION
   ASSEMBLY
                ESTIMATED
                BLOCKAGE
  ("SHADED AREA]
• |_ DUCT AHEA J
X  1C3.
  Figure  17-2.   Projected-area  model  of cross-section
  blockage  (approximate average for  a  sample traverse)
  caused  by  an  in-stack filter  holder-probe  extension
  assembly.
                                                                           O

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                                                                                  Section  No.  3.11.10
                                                                                  Revision  No.   0
                                                                                  Date  January   4,   1982
                                                                                  Page  5  of  11
  Delect a noezle size baaed on the range of
 velocity heads, such that tl Is net necessary
 to change the nozzle size in erder to main-
 tain isokinetlc euhpilng rates. Dunne  the
 run. do not change the nozzle ilz*. Ensure
 that the proper differential preuurt gauge
 li chosen tor tht range ot velocity heads en-
 countered (we Section 2.J of Method 3).
  Select a probe extension lenrth iuch that
 all traverse point* can be tampted. Per larrr
 etacks.  consider sampling  from  opposite
 tides of the  euek te  redue* the lencth of
 probes.
  Celect a tola) sampling time greater than
 er equal to  the .ralnimmn  total aampling
 time specified la the test procedures for the
 eperific Industry such that (1) Uv r«TVit
 time per point is not leu than 2 minutes tor
 tome rreiier tune  interval  If specified by
 the  Administrator), and (2) the  sample
 volume laker, (corrected to standard condi-
 tions) will exceed  the required minimum
 tstaJ gu (ample volume. The latter Is based
 en an approximate averatr sampling rate.
 ' It  b recommended  that  the  Dumber of
 minutes campled at each point be an inleeer
 er an integer plus one-half minute, in order
 to avoid timektepint error t.
• In some circumstances, e.g.. batch cycles.
 ft msy be necessary to sample for shorter
 times at the traverse points and to obtain
 cmaller cas Sample volumes. In these cases.
 the  Administrator's approval mus: first be
 obtained.
  4.1.3  Preparation ;ef  Collection Train.
 During preparation  arid assembly of  the
 tampltng train, keep all openings where con-
 tamination  etn occur  covered  until  just
 prior to assembly or unto sampllnc is about
 10 bctln.
  If  Imptnten are used to  condense  stack
 Cas moisture, prepare them as follovs: place
 100 ml of water In earh of the first tvo im-
 ptnren. leave  the third tepinger empty.
 ana  transfer approximately  500  to 300 I of
 preweighed  silica gel from Its container to
 the fourth implnier. More silica tel may be
 used, but care should be taken to ensure
 that it is not entrained and carried out from
 the  imptnger durlnr samplini. Place  the
 container in a clean place for later use in
 the  sample  recovery.  Alternatively,   the
 weight of the silica eel plus impinger  may
 be determined to the nearest 0.5 r and re-
 esrdid.                           •
  If  some means other  than implngen is
 used to condense 'moisture, prepare the con-
 Censer  (and.  If appropriate, silica gel  for
 csndenser outlet) for use.
  Using a tweezer or clean disposable surgi-
 cal elovei, place a labeled (identified) and
weighed filter in the filter holder. Be sure
that the filter is properly centered and the
fftskrl properly placed so as not to allow the
sample gas stream to circumvent the filler.
Check filter for tears after assembly is com-
pleted. Mirk the probe extension trtth heat
mutant tape or by some other method to
denote the proper distance Into the stack or
duct for .each sampling point.
  Assemble the train as in Figure 11-i. using
a very light coal of silicon? grease  en all
(round (lass joint* and  greasing only the
outer portion (see APTD-OS76) to avoid pos-
sibility  of contamination by the sllleone
'grease. Place crushed  ice around the to-
pingers.       >  '  .
  4.1.4 beak Check Procedures.
  4,1,4.1  Pretest teak-Check.  A  pretest
leak-check if recommended,  bul  net re-
quired. If the tester opts to conduct the pre-
test • leak-check,  the  following, procedure
(hall be used.
  After the sampling train has been assem-
bled, plug the irUf-t to the probe nozzle with
t material that will be able to withstand the
suck  temperature.  Insert the filter holder
into  the stack  and wait approximately  S
minutei (or  longer, if necessary) to allov
the system to come to equilibrium vith the
temperature  of the stack gas stream. Turn
on the pump and draw a  vacuum of at least
380 mm Hg (IS in. HIV.  note that a lover
vacuum may be used. provided that it is not
exceeded  during the  test. Determine  the
leakage rate. I.  leakage rate  In excets of 4
percent of  the  average  sampling rate er
O.OOOS7 m'/rnln. (0.02dm), whichever  is
less, Is unacceptable.
  The following leak-check instructions for
the sampling train described in AJTD-0578
and APTD-OSB1 may be  helpful. Start the
pump with by-pass valve fully open  and
coarse adjust valve completely  closed. Par-
tially  open  the coarse  adjust valve  and
slowly .close the by-pass  valve until  the de-
sired  vacuum It  reached. Do not reverie di-
rection of  by-pass valve. If  the  desired
vacuum is exceeded,  either  leak-check at
thls'hithtr vacuum or end the leak-check as
shown below and start over.
  When the leak-check  is completed, first
slowly remove the plug from the inlet to the
probe nozzle and immediately turn  off the
vacuum pump.  This prevents  water from
being forced backward and keeps silica gel
from  being entrained bsrkward.
  4.1.4.2  Leak-Checks During Sample Run.
If. during  the sampling  run, a component

-------
lOCATIOR.
OPERATOR.
DATE	
nun no.
SAMPLE UOXNO..
METER BOX no._
C FACTOR
riTOT TUDE COEFFlCIEflT. Cp.
OAROMETRIC PRESSURE.
ASSUMED MOISTURE. % _
POOOE EXTENSION LEfiGTH.nilfU.
nozzu IDENTIFICATION no	
AVERAGE CALIBRATED NOZZLE OlAMETEn. tmCln.l.
FILTER riO.	
LEAK nATE.mtymJn,(ttir|	
STATIC PRESSURE, mm HB (in. Hrf.
                                    SCHEMATIC OF STACK CROSS SECTION
TRAVtRSC POINT
Nuiwntn












TOTAl
SAKTIIKO
TIME
(01. mln.













AVI RAGE
VACUUM
tnm ll|
Cm. tit)














STACK
TEMPERATURE
.(TV-
•c j*ri














VEiocmr
HEAD
!Ars).
tnnHjO
(I«.ll20j














PftEKURE
OlFFintflTIAl
ACROSS
ORIFICE
METER.
mmlljO
(m.ll^O)














CAS SAMPLE
VOLUME.
PiJ tM3»














CAS SARWtE Tt^TtnATl/nC
AT OUT GAS METER
IMIET.
•C(«F)












A«(|
OUTLET.
•C (»F|












A«(|
Avg
TEKfERATURE
OF CAS
tEAVUlG
CONOEnSEROR
LASTIMPinctn.
•C I"F|














         o
                                           Figure 17-3. Paniculate ficWdala.
                                                                                                                         n* a id in
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                                                                                                                             W H-
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-------
                                                                                     Section  No.   3.11.10
                                                                                     Revision No.   0
                                                                                     Date  January  3,  1982
                                                                                     Page   7  of  11
  Clean the porthole* prior to the teat run
 lc minimize the chine* e! aarapllnt the de-
 posited material. TV berln sampling, remove
 the nozzle up and verify that the pilot lubt
 and  probe  extension   are  properly  poil-
 Uoned. Position the nozzle  it the first tra-
 vtrtf point with the tip pointing directly
 into  the  in stream. Immediately lUrt the
 pump and adjust the flow u tooklnetie eon-
 dllloru. Nomographs  trt available,  which
 aid tn the rapid adjustment  to the isoklnetle
 umpiint rue  «-lthout  excessive computa-
 tions ThtM nomographs are  designed  lor
 \ot when the Type S pilot tub* coefficient
 It  0.8Ss0.02.  and the stack tas equivalent
 density tory molecular  weight) Is equal  to
 2Jr4 AJTD-0516 detail* the procedure  for
 usinr the nomographs. If C, and M, are out-
 tide the above tuted rant«. do not use the
 nomofiphs unless appropriate steps (tee
 Ctution  1 In Section  t) are taken to com-
 pensate for the deviations.
  When the slack I* tinder ittnlfieaat  neja-
 Uve  precsun  (helrht  of Impinter «tem>,
 lake care to  dote the  coarse adjust  TaJve
 before  Inserting the probe extension mem-
 oir Into  the  stack  to  prevent  viler  from
 be tat  forced backward. 11  neeemjy. the
 pump  may be  turned  en vlth the come
adjust  rilvr closed.
  When the probe is in position, block  off
the openinrs around the probe and porthole
to prevent  unrepresentative dilution of the
tas streim.
  Traverse  the stack  cross  »ection,  is  re-
quired  by Method 1 or  is specified by the
Administrator,  beint cireful not to bump
the probe nozzle Into  the stack walls  Then
simsluig near the wills or when removtnt
or Inserting the probe  extension through
the portholes,  to minimize chince of  ex-
tracting deposited material.
  Durint the  test  run. tike  appropriate
steps (e.r.. addlnt crushed  lev to the 1m-
Pinter  ice bath) to maintain a temperature
of less  thin 30* C (88° F> it the condenser
outlet:  this will prevent excessive moisture
Josses. Also, periodically check the level and
tero of the manometer.
  If the pressure drop  across the filter  be-
comes too high, rnikinc Uokinelic sampllni
difficult to miinuin. the filter may  be  re-
placed  in the midst of  a simple run. It is
recommended thai another  complete  filler
holder  assembly be  used rather than  at-
tempting to chant e the filler Itself. Before a
new filler holder U installed, conduct a leak
check,  as outlined in Section 4.1.4.2. The
total paniculate welcht still  Include the
sumrr.r.ion of ill filler auembly catches.
  A single train shill be used for the entire
simple run. except in cases where simulta-
neous samplin;  is required in  two or  more
separate  ducts  or at two or more different
locations within the tame duct, or, in eases
where  equipment  failure   necessitates  a
ehante of trains. In all other situations, the
use of  two or more trains will be subject to
the  approval  of the Administrator.  Note
that  when  two or more trains  are used, a
separate  analysis of the collected partleu-
lite  from each train shall be performed.
unless  identical nozzle sizes  were used  on  all
 trains,  in which case the paniculate catches
 from tht individual trains may be combined
 and a Untie analysis performed.
  At the end of the sample run, turn oil the
 pump,  remove the probe extension assembly
 from the stack, and record the final dry tas
 meter readlnt. Perform  a leak-check, as out-
 lined in Section 4.1.4.3. Also, leak-check  the
 pilot lines u  described in Section  S.I  of
 Method  S; the  lines  must  pau this leak-
cheek, in order to validate the velocity bead
data.
  4.1.6  Calculation  ef  Percent  Uoklnetlc.
Calculate percent  Uokinetic  (see  Section
6.11) to determine whether another test run
ahould  be  made. If there is difficulty  In
snalntalnini iioklnetlc rates  due  to  aource
condition*, consult  with the  Administrator
for possible variance on the isoklnetlc rales.
  4.2 Sample  Recovery. Proper  cleanup
procedure betins as soon as  the  probe  ex-
tension auembly U removed from the tlark
tst the end of the sampling period. Allow the
assembly to cool.
  When the auembly can be safely handled.
wipe off all external paniculate matter near
the Up  of the  probe code and place a cap
over it to prevent losing or ralnlnt panicu-
late matter. Do  not cap off  the  probe  tip
Uchtly  while the aamplint train  is eoolini
down u this vould create a vacuum in the
filter holder, fordnj coBderuer viler back-
ward.
  Brfor* mortnt th* (ample train  to the
cleanup live, cUsconneci the filter  bolder-
probe nozzle aaembly from  the  probe  ex-
tension: cap the  open inlet of the probe  ex-
tension. Be careful  Dot  to Icxe an? oonden-
aaie. If  present.  Remove the  umbilical cord
from the condenser outlet  and  cap the
outlet. If a flexible  line is xued between the
first impinter  (or condenser)  and the probe
extension, disconnect the line at  the probe
extension and let  any condensed waier  or
liquid driia into the Impiniers or condens-
er. Disconnect the probe extension from the
condenser:  cap the probe extension  outlet.
AJler wlplnt off the tUicone  treue. cap off
the condenser inlet. Oround  glass stoppers.
plastic cap*, or  serum caps (whichever  are
appropriate) may  be used  to  close  these
openints.
  Transfer   both  the  filter  holder-probe
nozzle auembly and the condenser to the
cleanup area. This area should be clean and
protected from the wind so thai the chances
of conlajninaUnt or loslnt the sample will
be minimized.
  Save  a portion of the acetone used  for
cleanup as a blank. Take 300 ml of this ac-
etone directly from the wash bottle beint
used and place It in a class aunple container
labeled  "acetone blank."
  Inspect the train prior to and  durlnt dis-
assembly and note any abnormal conditions.
Treat the samples as follows:
  Cor.Jelner No. 1. Carefully remove the
filter from the filler holder and place it in
Its identified petrl dish container. Use a pair
of tweezers and/or  clean disposable  surtical
(loves to handle the filter. If It 1s necessary
to fold the filter, do so such that the panic-
ulaie cake is inside the fold. Carefully trans-
fer to the petri dish any paniculate matier
and/or  filter  fibers which  adhere  to  the
filter holder rasket. by  usint a dry Nylon
bristle brush  and/or a  sharp-edted blade.
Seal the container.
  Container tto.  2.  Takint care to *ee that
dust on the ouutde of  the probe nozzle or
other exterior surfaces does not tet into  the
sample, quantitatively  recover  paniculate
matter  or any condensite from  the probe
nozzle,  fltilnt. and from half of the filler
bolder bx washlnj these components with
acetone and placinc the wazh in a ilass con-
tainer. Distilled  water may be used insteid
of acetone  rhen approved by the Adminis-
trator end shall be used when specified  by
the  Administrator: in  these eases,  save  a
viler blank and follow  Administrator's  di-
rections on analysis. Perform the  acetone
      u follows:
  Carefully remove the probe  notzle  and
clean the inside surface by rinslnt wiih ac-
etone from a wuh bottle and brushing with
a Nylon bristle brash.  Brush until acetone
rinse shows no visible panicles,  afier which
make a final rinse of the inside surface vlih
are lone.
  Brush and rinse with acetone the inside
paru of the titling in a similar way unill no
visible panicles remain. A funnel (glais or
polyethylene) may be used to kid in trans-
ferring liquid washes to the container. Rinse
the brush  with acetone and Quantitatively
collect thete  washints  In the aarnple  con-
tainer.  Between   aamplint   runs,  keep
brushes clean and protected from conu.rr.l-
nation.
  AJver  ensuring  that  all joints are wlpvd
clean ef lillcone create (If applicable), clean
the inside  of the front half of  the filter
holder by rubbing the surfaces with a Nylon
bristle  brush  and rinsing  with  acetone.
Rlrute MCh surface three Umet or more If
&e*o«d to remove visible paniculate. Make
final rinse of the brush and filter holder.
ATVer all acetone vasrjots *nd paniculate
Batter are collected la  the umple contain-
er, lighten the lid on the simple container
so that acetone will not leak out when II Is
(hipped to the laboratory. Mark the height
ef the fluid level to determine whether or
not  leakage   occurred durlnt  transport.
Label the  container to clearly Identify its
conlents.
  Container Ho. 3. if til lea fel U uted in the
condenser  system for mocliure content de-
termination, note the color of the gel to de-
termine tf it  has  been completely ipent:
make a notation  of its condition. Transfer
the illiot  gel back to its original container
and  Kil.  A funnel may make tt easier to
pour the  silica gel without spilling, and  a
rubber policeman may be used as an aid in
removing the silica gtl. It Is not necessary to
remove  the small amount of dust panicles
that may  adhere  to the walls and are  diffi-
cult  to remove. Since the tain In weight is to
be used for moisture calculations, do not use
any  water or other liquids to  transfer the
alllca te).  If  a balance Is available tn the
field, follow  the procedure  for  Container
No. S under "Analysis."
  Condenter Waier. Treat the condenser or
Ixnplnter water as follows: make a notation
of any color or film in the liquid catch.  Mea-
sure the liquid volume to within =1 ml by
usinc » rraduaied cylinder or. If a balance is
available,   determine  the liquid  weight to
within ±0.5 g.  Record  the total  volume or
weight of  liquid present. This Information is
required to calculate the moisture content
of the effluent gas. Discard the liquid  after
measuring and  recordmt the volume  or
weight.
  4.3 Analysis. Record the data required on
the  example sheet shown In  Figure  17-4.
Handle  each sample container *x follows:
  Container No. 1. Leave the contents in the
shipping container or transfer the filter and
any  loose paniculate from the simple con-
tainer to a tared  tlass  weighing dish. Desic-
cate for 24 houn in a  desiccator containing
anhydrous calcium sulfate. Weigh to a con-
stint weight and report the results to the
Dearest  0.1 mg. Tor purpose* of this Section.
4.3. the term "constant weight" means  a dif-
ference of no more than 0.5 mt or 1 percent
of total weltht less tare weight, whichever to
greater, between  two consecutive weighings.
with  no less than e  boun  of desiccation
time between welghlnn.
  Alternatively,  the sample  may be  even
dried at the  avervge stack temperature or
                                                                                                  '
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                                                                   Coction No.  3.11.10
                                                                   Revision No.  0
                                                                   Date  January  4,  1982 x-^
                                                                   Page  8  of  11            f  )
1CV C (SW F). whlchtw to teu. tor S
fcsun, eaolrt in tht dule&ier. wri wel
la A eonsUAl *ettht. unltu oihcrwbf «wrl-
    by 'tbt'AteiWslmler. Tht Ustar taay
   » 'opt ta 6v«n dr>- thr earaple « ">«»*«;•
t3t »utk tempmuiw cr ley C CIW* P».
chtehevcr to lea. ler s ta l.heun. wish the
einpu. ta« .«».this.tr?»8ht u  a.flnal.
Plant.

Dots.
Hun f Jo.,
Fator No.
                                   Amount liquid I tit durin| troniport

                                   Aotoni blank volume, nl

                                   Aotons tvtsh voluns, tnl____
                                   Aeotoni block concentration, mg/mg (equotion

                                   Aettone v/ath blink, mg (equrtion 17*6) -
                                      CONTAINEH
                                       Nuwcen
                                        TOTAL
                       WEIGHT O? PAfTTICULATE COLLECTED.
                                  /'   'lag.
                                                     FINAL WEIGHT
                                   TAHE WEIGHT
                                                           Loot ocotono blcnh

                                                           Height of portieuInto manor
WEIGHT GAIN
                                                                                               o


FINAL
INITIAL
LIQUID COLLECTED
TOTAL VOLUME COLLECTED
VOLUME O? LIQUID
WATER COLLECTED
IMPINGER
VOLUME.
ml




SILICA GEL
WEIGHT.
0



0' ml
                                         * CONVERT WEIGHT OF WATER TO VOLUME OY DIVIDING TOTAL W
                                          INCREASE DY DENSITY OF WATER (In/ml).

                                                                      INCREASE. Q
                                                                                 « VOLUME WATER, ml
                                                             Figure 17-4. Anolyticol data.

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                                                                                   Section  No.  3.11.10
                                                                                   Revision  No.  0
                                                                                   Date  January  4,  1982
                                                                                   Page  9  of  11
  Container No. i. Note the level of liquid In
t&a eonUincr and confirm en the analysts
C&Mt whether or -cot leakage  occurred
•total transport. If a noticeable amount of
tsakoce hu occurred, either void the sample
er use methods, subject to the approval of
the Administrator, to  correct the final re-
ruiu. Meature the liquid In  this container
either volumetrically to ±1 ml or gravime-
tricolly to ±0.5 t- Transfer the conunu to a
tared 250-ml beaker tnd evaporate to dry-
Bess at ambient temperature and pressure.
Desiccate for 24 hours and welch to a con-
cs&nt weight. Report the result* to the near-
est 0.1 mg.
  Container No. S. This *tep may>b* con-
Carted to  the field. Welch the spent ctllca
rsl (or silica eel plus implneer) to the near-
est 0.5 f uitnt a balance. ,
  "AettoM HlonJt" Container. Measure ac-
etone In this container either volumetrtcally
er eravimetrically. Transfer the sceton« to a
tared ISO-mi Maker and evaporate to dry-.
ess at ambient temperature and pressure.
Dssteeate for 34 hours and welch to a eon-
Cant weight, neport the resulu to the near-
est 0.1 »c.
  Nots.—At the option  of the Utter, the
csnUnu of Container No. 2  as well ts the
ttttone blank container may be evaporated
bt temperatures hither than  ambient. If
evaporation is done at an elevated tempera-
tare,  the  temperature  must be  below the
tailing point of the solvent: also,  to prevent
"bumplnc." the evaporation process must be
dtttsly supervised, and the contents of the
bsaker  must  be swirled  occasionally  to
caintoin an even temperature. Use extreme
eve,  as acetone is  highly flammable and
fcas a low flash point.
  I. Calibration. Maintain a laboratory toe
el all calibrations.
  S.I  Probe Nozzle. Probe nozzles shall be
calibrated  before their Initial use  In the
CsW. Usinc  a micrometer, measure  the
      diameter of the nozzle to the nearest
 0.025 mm (0.001  In.). Make three separate
 measurement*  using  different  diameters
 each time, and obtain the average;of the .
 measurement*. The difference between the
 high and low numbers shall not exceed 0.1
 mm  «<0.004  in.). When  nozzles  become
 nicked, dented, or corrode!  they shall be
 reshaped,  sharpened,   and   recalibrated
 before use. Each nozzle shall be permanent-
 ly and uniquely Identified.
  6.S Pltot Tube. If the pilot tube is placed
 to an Interference-free arrangement with re-
 epect to the other probe assembly cosipo-
 sent*. Its baseline (bolat«d tuba) coefficient
 shall be determined ta outlined la Section 4
 of Method 2. If the probe oessably is not in-
 terference-free, the pitot tube assembly co-
 efficient shall be  determined by calibration.
 usinc methods subject to the approval of
 the Administrator.
  5.3 Meurinc Sysum. Before  its initial
 use In the field,  the meterlac system shall
 bt calibrated accordlnc  to the  procedure
 outlined In APTD-0578. Instead of physical-
 ly adlustine the dry cas meter dial readings
 to  correspond to the wet test meter read-
 ings, calibration  factors  may be ussd to
 mathematically correct the CBS meter dial
 readings to the proper values.
   Before calibrating the mettrinc system, it
 Is succested  that a leak-check be conducted.
 For  meterinc systems  havine dlaphraem
 pumps, the normal leak-check  procedure
 will  not detect leakacta within the pump.
 For  these casa  the followiac  leak-cheek
 procedure is succeeted:  .make a 10-minute
 calibration..run  at  0.00057  mVmin (0.02
 cfm); at the  cad  of the run, take the differ-
. enee of the measured wet test meter aad
 dry cos meter volumes divide the difference
 by 10.  to c«t the leak rate.  The leak rate
 should not  exceed 0.00057  n'/taln (0.03
 cfm).                      '
  After each field use. the calibration of the
 metertnc system ahall.be checked by per-
 fonninc three calibration runs at a single.
 intermediate orifice setting (based on  the
 previous field test), with the vacuum set'at
 the maximum value, reached during the tfest
 series. To adjust the vacuum, insert a valve
 between the wet test meter and the inlet of
. the' meterinc system. Calculate the avertee
 value of the calibration factor. If the, call:
 bration  has chanced by more than 5. per-
 cent, recalibrate  the  meter over,  the full
 ranee of  orifice settings,  as outlined  in
 APTD-OS76.
   Alternative procedure*, e.g., using the ori-
 fice meter coefficients, may be used, subject
 to the approval of the Administrator.

   More.—If the  dry cas  meter coefficient
 values  obtained before and after a test
 series differ by  more than 5 percent, the
 test csrles shall either be voided, or calcula-
 tions for the teat aeries shall be performed
 using whichever meter  coefficient value
 (i.en before or after) elves the lower value of
 total sample volume.
   S.4 Temperature Gauges.  Use the proce-
 dure in  Section 4.3 of Method 2 to calibrate
 in-stock temperature gauges. Dial thermom-
 eters, such  as are used for the dry gas meter
 and  condenser  outlet, shall  be  calibrated
 against  mercury-in-class thermometers.
   5J Xieok Check  of Metering   System
 Shown  in  Figure 17-1. That portion of the
 sampling train from the pump to the orifice
 meter should be leak checked prior  to initial
 use and after each shipment. Leakage  after
 the pump will result in less volume  being re-
 corded than is actually sampled. The follow-
 ing procedure Is suggested (see Figure 17-5).
 Cloae the  main valve on the meter box.
 Insert   a   one-hole rubber  stopper  with
 rubber  tubing attached into the orifice ex-
 haust pipe. Disconnect and vent the low side
 of the orifice manometer. Close off the low
 aide orifice tap. Pressurise the system  to 11
 to 18 cm (5 to 7 in.) water column  by blow-
 ing  into the rubber tubing. Pinch off the
 tubing and observe  the manometer for one
 minute. A loss  of pressure on the mano-
 meter Indicates a leak in  the meter box:
 leaks, if present, must  be corrected.

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a>
«*
a>
E
in
fi
 u

 I
                         Section  No.   3.11.10
                         Revision No.  0
                         Date  January  4,   1982
                         Page  10  of  11
  I.I  Barometer. Calibrate against a tacr>
eury barometer.
  C. Calculation*. Carry out calculation*. «•
taintnf at leaii one  extra decimal flrure
fctyond that ol the acquired ftau. nound eft
fijuro after  the  final ealculatlen. Other
forms of the equations nay be uMd a* Ions
U thry rtvt equivalent rtaulU.
  8.1  Nomenclature.

A.»Croes-»ectlona) am of nesJc. ia> (f t>).
IU- Water vapor in the n>* dream, proper*
   tlon by volume.
C.»Ae9U>nt  blank mtdue  concentration,
   mi/f.
^-Concentration of  paniculate matter In
   stack  ras. (Sry b&iU. corrected to run-
   tlard eoneSiUoaj. i/dscm (c/daef).
I •Percent of boklnetle cunpllru.
U'UaxtnuR-.  aeeepublr  leakict rate  for
   either a preteit leak cheek or for a leak
   check  follovtnt  a eamponsnt  chanif;
   CQual to O.OOOS7 n'/nin (0.03 efra) or 4
   percent of the average fompllns rau.
   whlehe\-«r U )e=i.
!,• Individual leakatr rate observed fiurtni
   the leak check conducted prior to  the
   -1*" component ehanse (I - 1. 2. 1 . . . nl.
   m'/min (cfm).
L,>Leakai«  rate oeaerved durinr the post-
   tut leak check., m'/iain (dm).
ni.. Total amount of paniculau natter eal-
   lecled. mi.
U.. Molecular weight of cater. 11.0 lit'
   mcltUt.Olb/lb-nolt).
m.»Mui of residue of acetone after evapo-
   ration. mi.
Pw'Darometrlr pressure at the aampllnt
   tlu, mm lie ttn-Hii.
P. -Absolute itack c« pressure, ton Ux (ta.
   Ue>.
PM»Ctandard absolute pressure, tto  nn
    lie (21.92 In. He).
R« Ideal  cat eonstar.t. 0.05236 ma Hr-ciV
    •K-r-molf (JI.65 in. Ht-ft'/'R-lb-mole).
T.-Abioluw averatr dry r&s meter tem-
    perature (»« Firure 17-j). TE (111.   '
T,«Ab*e)ute averate (lack cas tamperaturt
    (see rtrure 11-J), TC CHI.
T.,- Standard absolute temperature. 1»J'K
                                            o
                                                                   o
                      V.-Volum« of aeetene blank, ml.
                      V.. -Volume of acetone used In vain. ml.
                      Vk*Teial volume of liquid collected in 1m-
                         plncen  and silica (el (see Firure 17-4).
                         ml.
                      V.- Volume of rat sample as measured by
                         dry »aj meter, dcm (def ).
                      V»wi"Volume of  tu sample measured by
                         the dry  tu meter, corrected to standard
                         conditions, diem (dicf ).
                      VwMi-Voiut.it of  water vapor in the fas
                         cample,  corrected  to   standard condi-
                         tions. scm (scf ).
                      v,» Stack ru velocity, calculated by Method
                         2. Equation 2-9. uslnt data obtained
                         from Method 17. m/sec (ft/sec).
                      W.-Welfht of residue in aretone rain. mt.
                      V-Dry (u mner calibration coefficient.
                      AH- Avert u pressure  differential across
                         the  orifice meter (see  Firure 17-31. mm
                         K,O (in. H.O).
                      f.- Density of acetone, mi /ml (tee label on
                          bottle).
                       c.« Density of water. 0.9982 i/ml (0.002301
                          Ib/ml).
                      (-Total simpllnr time, mln.
                      «,-.S»mpllnr time Interval, from the berin-
                          n'.nc of a run  until the first component
                          chante. mln.
                      1,-Sunpllnr time  interval,  between two
                          successive  component ch antes, berin-
                          nlni with the  interval between the firtt
                          and second chaiuai. ctia.
                                               o

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                                                                              Section  No.   3.11.10
                                                                              Revision No.  0
                                                                              Date  January  4,   1982
                                                                              Page  11  of  11
            Urn* tnUTTtl. frwa tht HruO
   (a*) component ehanfft uatfl the cad of
   tht tampllnj run, "*'"-
!&6<.Dp*etfle entity et tasreury.
IC9> Con version te ptresnt.

  &> Averwe «lry rai racier temperature
tad avcrwc oritktt prvuure flrop. CM d*U
  
                                                             tcetlon  Acency.  Aetcarch Trtvnsli ftj-k,
                                                             n.C. ATTD-OS7«. March. 1(72.
                                                               4. Bmlth, W. C.. n. T. Bhlrthut.  uid W.
                                                             I*. Todd. A Uethod of  InterpreUnt Cuek
                                                             Bunpllnr D«U. Fiper Tmenud at the llrt
                                                             Annual  Heettnt ef tht  Air FoUulten  Con-
                                                             trol AuociaUea. Eu LouU, Me. Juna 14-lt.
                                                             inc.
                                                               I. Cmlth, V7. B., et •!.. Buck OM OunpUas
                                                             Iiaprovcd  and BimplUled with  Mew Equip-
                                                             tMM. APCA Paper No. (7-111. 1M7.
                                                               6. OpveUle&ileni (or Incinerator Tcstlnc ftt
                                                             PMleral ncUitin. riiB. KCA7C. 1017.
                                                               7. Bhiteharv  R.  T. Adjuitmenu tn the
                                                             EPA Hoaocraph (or DUIertfit Pilot Tub*
                                                             Coefficient! and Dry Molecular Weights.
                                                             Buck Campllnf Netn 2:4-11. October. It74.
                                                               (. Vollare. R. r. A Survey et Commcrclb]-
                                                             ly Available Inttrumcnutien (er the  Hea-
                                                             (urement et Lew.Ruue  Ow VeleelUea. DJ5.
                                                             EnvironmcnUl Protectlen Artney. EatUslen
                                                             Ueuurement Branch.  Reteareh Ttlantlt
                                                             Pwt. N.C. November.  l»7t (uapubltibed
                                                             paper).
                                                               t. Annual Book of ASTM Bundards. Pvt
                                                             SI. Oa«*out rucks: Coal and Cokt; Atme-
                                                             ephtric Analyst*. American ttoclety (er Test-
                                                             tAi and UaUrtsOs. PtUJadtlphU, Pa.  1174.
                                                             pa (17-62X
                                                               10. Vellare, H. 7. neeomaended Pree»-
                                                             tfurt (or Sample Travtnes ta Cnieu Smaller
                                                             than 13 Inches  ta  DU0»t*» VJ. Cnvfron-
                                                             tatnUl  Preuctlen  Artncy, Etntulen  Mea-
                                                             eurement  Branch. Kaeiftti Triansle Park,
                                                             >f.C. November. »!*•
                                                                               (Ote.  114. CIru Air Aft
                                                                               TJJS.C.7414)).**7*1
                                                                                                           U
                                                                                                                      «I
 tad tubstltuie only lor those leakare rates
 
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                                             Section No.  3.11.11
                                             Revision No.  0
                                             Date January 4,  1982
                                             Page 1 of 1
11.0  REFERENCES

     1.    Standards of Performance  for New  Stationary  Sources,
          Federal Register, Vol. 43, No.  37,  February 23,  1978.

     2.    Martin,  R.  M.   Construction  Details  of  Isokinetic
          Source Sampling Equipment.  Publication No.  APTD-0581.
          Air Pollution  Control Office,  EPA, Research  Triangle
          Park,  N.C.,  1971.

     3.    Rom, J. J.  Maintenance,  Calibration,  and Operation of
          Isokinetic Source Sampling Equipment.   Pub. No.  APTD-
          0576.   Office of Air  Programs,  EPA,  Research Triangle
          Park,  N.C.,  1972.

     4.    Mitchell,  William  J.,  M.   Rodney  Midgett,   and  C.
          Bruffey.  Comparative Testing of EPA  Methods  5 and 17
          at  Nonmetallic  Mineral  Plants.    EPA-600/4-80-022.
          U.S.  Environmental  Protection  Agency,  Research  Tri-
          angle Park,  N.C., April 1980.

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                                             Section No. 3.11.12
                                             Revision No. 0
                                             Date January 4, 1982
                                             Page 1 of 1
12.0  DATA FORMS

     Blank data  forms are in Method  5,  Section 3.4.12,  for the

convenience of the Handbook user.  All forms are the same as for
Method 5 "with the exception of Figures 3.1 and 4.5 which are in-

cluded in Method Highlights, Section 3.11.

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April 1983
1
Section 3.12.0
        United States
        Environmental Protection
        Agency
        Research and Development
                  Environmental Monitoring Systems
                  Laboratory
                  Research Triangle Park NC 27711
                  EPA-600/4-77-027b  Feb. 19£A
        Section  3.1
        Method  9—Visible
        Opacity  of  Emissions from
                                   Outline
        Section
        Summary
        Method Highlights
        Method Description
         1. Certification and Training of
           Observers
         2. Procurement of Apparatus and
           Supplies
         3. Preobservation Operations
         4. On-Site Field Observations
         5. Postobservation Operations
         6. Calculations
         7. Auditing Procedures
         8. Reference Method
         9. References and Bibliography
        10. Data Forms
                                       Number
                     Documentation   of Pages
                         3.12.0             2
                         3.12.0             2
                         3.12.1

                         3.12.2
                         3.12.3
                         3.12.4
                         3.12.5
                         3.12.6
                         3.12.7
                         3.12.8
                         3.12.9
                         3.12.10
                          2
                          2
                         18
                          2
                          7
                          2
                          5
                          1
                          9
        Summary
          Many stationary sources discharge
        plume-shaped visible emissions into
        the atmosphere. Method 9 (EPA
        Reference Method) is used to
        determine the opacity of this plume by
        qualified observers. The method
        includes procedures for the training
        and certification of observers and
        procedures to be used by these
        observers in the field to determine
        plume opacity. This section of the
        Quality Assurance (QA) Handbook
        primarily concerns procedures used by
        the observers. Only Section 3.12.1
        reviews the training and certification
        procedures, which are described in
        Reference 1.
                   The appearance of a plume as
                 viewed by an observer depends upon
                 a number of variables, some of which
                 may be controllable and some of
                 which may not be controllable in the
                 field. Variables which can De-
                 controlled to an extent to which they
                 no longer exert a significant influence
                 upon plume appearance include:
                 angle of the observer with respect to
                 the plume; angle of the observer with
                 respect to the sun; point of
                 observation of attached and detached
                 steam plumes and angle of the
                 observer with respect to a plume
                 emitted from a rectangular stack with
                 a large length to width ratio. The
                                                       ,-V^

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                      Section 3.12.0
                                  April 1983
method includes specific criteria
applicable to these variables.
  Other variables which  may not be
controllable in the field are
luminescence and color contrast
between the plume and the
background against which the plume
is viewed. These variables exert an
influence upon the appearance of a
plume as viewed by an observer, and
can affect the ability of the observer
to accurately assign opacity values to
the observed plume. Research studies
of plume opacity have demonstrated
that a plume is most visible and
presents the greatest apparent opacity
when viewed against a contrasting
background. It follows  from this, and
is confirmed by field trials, that the
opacity of a plume, viewed under
conditions where a contrasting
background is present can be
assigned with the greatest degree of
accuracy. However, the potential for a
positive error is also the greatest
when a plume is viewed under such
contrasting conditions. Under
conditions presenting  a less
contrasting background,  the apparent
opacity of a plume is less and
approaches zero as the color and
luminescence contrast decrease
toward zero. As a result, significant
negative  bias and negative errors can
be made  when a plume  is viewed
under less contrasting conditions. A
negative  bias decreases  rather than
increases the possibility that a plant
operator will be cited for a violation of
opacity standards due to observer
error.

  Method 9 is applicable for the
determination of the opacity of
emissions from stationary sources
pursuant to 60.11(b). Studies have
been undertaken to determine the
magnitude of positive  errors that
qualified  observers can  make while
reading plumes under contrasting
conditions and using the procedures
specified in Method 9. The results of
these studies, which involve a total of
769 sets of 25 readings  each, are as
follows:

  1. In the case of black plumes, 100
     percent of the sets  were read
     with positive error of less than
     7.5 percent opacity; 99 percent
     were read with a positive error of
     less than 5 percent opacity.
  2. In the.case of white plumes, 99
     percent of the sets  were read
     with a positive error (higher
     values) of less than 7.5 percent
     opacity;  95 percent were read
     with a positive error of less than
     5 percent opacity.
  The positive observational error
associated with an average of twenty-
five readings is therefore established.
The accuracy of the method must be
taken into account when determining
possible violations of applicable
opacity standards.
  Note: Proper application of Method
9 by control agency personnel in
determining the compliance status of
sources subject to opacity standards
often involves a number of
administrative and technical
procedural steps not specifically
addressed in the Federal Register
method. Experience has shown these
steps are necessary to lay a proper
foundation for any subsequent
enforcement action. To clearly
delineate items that are EPA
procedural policy and requirements of
the Method  9 from additional quality
assurance procedures, a wording
scheme was developed. All of
Sections 3.12.1, 3.12.2, 3.12.3,
3.12.6, and  3.12.7 are suggested
quality assurance procedures except
where noted as EPA policy or Federal
Register citings. Section 3.12.4  notes
EPA requirements with directive
statements  using words such as shall,
should, and must. QA procedures are
noted either with suggestive
statements  using words such as
recommended, suggested,  and
beneficial or by stating that the entire
subsection is recommended. The use
of these QA procedures should
provide a more consistent  program,
improved observer effectiveness and
efficiency, and improved data
documentation.

Method Highlights
   Section 3.12 primarily describes
Method 9 procedures for the
determination of plume opacity.
Section 3.12.1 briefly reviews the
quality assurance procedures to be
used in the observer training and
certification procedures described in
detail in Reference 1. The  remaining
sections describe the field procedures.
   Section 3.12.10 provides blank data
forms recommended for use by the
observer and other personnel, as
required. Partially completed forms,
are included in Sections 3.12.1
through 3.12.7.of the Method
Description. Each form in Section
3.12.10 has a subtitle (e.g.. Method 9,
Figure 2.1)  to allow easy reference to
the corresponding completed form.
   The following paragraphs present a
brief discussion of the contents of this
section of the QA Handbook.

 1.  Certification and Training of
 Observers The primary purpose of this
section is to provide a brief summary
of the certification and training
procedures described in Reference 1.
It includes a definition and a brief
history of opacity, and it discusses
observer training procedures and
certification and recertification of
observers.

2.  Procurement of Apparatus and
Supplies Section 3.12.2 presents
specifications criteria and design
features to aid the procurement of
useful equipment that would provide
good quality visible emissions data.
The following are some recommended
equipment items not specifically
required by Method 9: watch,
compass, range finder, Abney level or
clinometer, sling psychrometer,
binoculars, camera, safety equipment.
clipboard, and accessories. Table 2.1
summarizes the quality assurance
aspects of equipment procurement
3.  Preobservation Operations
Section 3.12.3 summarizes the
preobservation activities: gathering
facility information, providing prior
notification, establishing protocol, and
performing equipment checks. Table
3.1 summarizes these procedures.

4.  On-Site Field Observations
Section 3.12.4 contains detailed
procedures for determining the visible
emissions (VE). This section not only
includes the recommended
procedures for performing the
perimeter survey, plant entry, and VE
determination; it also contains a
subsection on special observation
problems. This subsection explains
how to take VE readings under less
than ideal  conditions (e.g., when the
observer position is restricted). The
main feature of this section is the
presentation of detailed instructions
on how to complete the recommended
VE data form, and examples of
completed forms.

5.  Postobservation Operations
Section 3"12.5  presents a brief
discussion concerning the data
reporting procedures, data summary,
data validation, and equipment check.
Section 3.12.6 contains a discussion
of the calculations required for
completing the data forms and
reports. It also  includes procedures  for
calculating the path length through
the plume and for predicting steam
plume formation by use of a
psychrometric chart and pertinent
measurements.

6.  Auditing Procedures Section
3.12.7 recommends performance and
system audits for use with field VE
determinations. The two performance
o
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 o

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                            April 1983
Section 3.12.0
audits are an audit by senior
observer/supervisor and a data
calculation audit. A system audit is
suggested, along with a Method 9
checklist, as shown in Figure 7.1.
Table 7.1 summarizes the quality
assurance activities for audits.

7.  References and Bibliography
Sections 3.12.8 and 3.12.9 contain
the Method 9 and suggested
references and bibliography.

8.  Data Forms Section 3.12.10
provides blank data forms which can
be taken from the QA Handbook for
field use or serve as the basis of a
revised form to be used by the
Agency. Partially completed forms are
included in the corresponding section
of the QA  Handbook.

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o
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                            April 1983
                                                                          Section 3.12.1
                           1.0 Certification and Training of Observers
  The purpose of this section is to
summarize the content of the QA
manual for VE training programs.1
Since the observer must be properly
certified or a qualified VE reader in
order to have his/her opacity reading
accepted, it is important that he/she
fully understand this phase of his/her
training.

1.1  'Definition and Brief
History of Opacity
  The VE evaluation system evolved
from the concept developed by
Maximillian Ringelmann in the late
1800's, in which a chart with
calibrated black grids on a white
background was used to measure
black smoke emissions from coal-fired
boilers. The Ringelmann Chart was
adopted by the U.S. Bureau of Mines
in the early 1900's and was used
extensively in efforts to assess and
control emissions. In the early 1950's,
the Ringelmann concept was
expanded to other colors of smoke by
the introduction of the concept of
"equivalent opacity."
  The Federal government has
discontinued the use of Ringelmann
numbers in EPA Method 9 procedures
for  New Source Performance
Standards (NSPS). Current procedures
are based solely on opacity. Although
some State regulations still specify
the use of the Ringelmann Chart to
evaluate black and gray plumes, the
general trend is toward reading all
emissions in percent opacity.
  In practice, the evaluation of opacity
by the human eye is a complex
phenomenon and is not completely
understood. However, it is well
documented that visible emissions
can be assessed accurately and with
good reproducibility by properly
trained/certified observers.
  The relationships between light
transmittance, plume opacity,
Ringlemann number, and optical
density are presented in Table 1.1. A
literal definition of plume opacity is
the degree to which the transmission
of light is reduced or the degree to
which visibility of a background as
viewed through the diameter of a
plume is reduced. In terms of physical
optics, opacity is dependent upon
transmittance (I/I0) through the
plume, where I0 is the incident light
flux and I is the light flux leaving the
plume along the same light path.
Percent opacity is defined as follows:
    Percent opacity = (1-l/U) x 100.
  Many factors influence plume
opacity readings: particle density,
particle refractive index, particle size
distribution, particle color, plume
background, path length, distance and
relative elevation to stack exit  sun
angle, and lighting conditions. Particle
size is particularly significant
particles decrease light transmission
by both scattering and direct
absorption. Thus, particles with
diameters approximately equal to the
wavelength of visible light (0.4 to 0.7
/urn) have the greatest scattering effect
and cause the highest opacity.

1.2  Training of Observer
  Field inspectors and observers are
required to maintain their opacity
evaluation skills by periodically
participating in a rigorous VE
certification program. Accordingly,
EPA's Stationary Source Compliance
Division (SSCD) and Environmental
Monitoring Systems Laboratory
(EMSL) have provided the QA training
document1 to individuals who conduct
VE training and certification programs.
This section summarizes the training
program.

1.2.1  Frequency of Training Sessions
— Certification schools  should be
scheduled at least twice per year
since Method 9 requires a semiannual
recertification. It  is highly
recommended that training be an
Table 1.1. Comparison of Light. Extinction Terms
Light Optical density Plume
transmission, % units opacity. %
O
20
40
60
80
100
N/A*
0.70
0.40
0.22
0.10
0.00
100
80
60
40
20
0
Ringelmann
number
5
4
3
2
1
0
*N/A = not applicable.
integral part of the certification
program.  A spring/fall schedule is
preferable because of weather
considerations. Certifying previous
graduates while the smoke school is
in session is more efficient and less
costly than scheduling a separate
session.
7.2.2  Classroom Training — The
training is accomplished most
effectively by holding an intensive 1 -
or 2-day classroom lecture/discussion
session. Although this training is not
required,  it is highly recommended for
the following reasons:
  1. Increases the VE observer's
     knowledge and confidence for the
     day-to-day field practice and
     application.
  2. Reduces training time required
     to achieve certification.
  3. Trains the smoke reader in the
     proper recording and
     presentation of data that will
     withstand the rigors of litigation
     and  strengthens an agency's
     compliance and enforcement
     program.
  4. Provides a forum for the periodic
     exchange of  technical ideas and
     information.
  Some states require classroom
training for initial certification only. It
is recommended,  however, that
observers attend the classroom
training at 3-year intervals to review
proper field observation.techniques
and method changes and to
participate in the  exchange of ideas
and new  information.

7.2.3  Lecture Material — Example
lecture material for a thorough
training program is presented in
Section 3.1 and Appendix A of
Reference 1. A typical six-lecture
classroom training program consists
of the following:
  Lecture 1—Background, principles,
             and theory of opacity.
  Lecture 2—Sources of VE's,
             presented by someone
             thoroughly familiar with
             source conditions,
             related particle
             characteristics, and
             opacity reading
             procedures and
             problems.
  Lecture 3—Proper procedures for
             conducting field
             observations under a
             variety of conditions.
                                                                                                     7

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                         Section 3.12.1
                                    April 1983
  Lecture 4—Influence and impact of
             meteorology on plume
             behavior.
  Lecture 5—Legal aspects of VE and
             opacity measurements.
  Lecture 6—Actual
             observation/testing
             procedures.

 7.2.4  Training Equipment — An
 integral part of the training program  is
 the design and operation of the smoke
 generator and its associated
 transmissometer, as specified in
 Method 9 (reproduced in Section
 3.12.8). Such a program is essential
 because proper observer certification
 cannot take place without the proper
 equipment. Section 4 of Reference 1
 presents  performance specifications
 and operating procedures for smoke
 generators which, if followed under a
 good QA program, will ensure
 nationwide uniformity and consistency
 with Method 9 criteria.
  The design and operation of the
 smoke generator has evolved.
 significantly since the mid-1960's.
 The basic components of the smoke
 generator now include:
  1. Black and white smoke
     generating units,
  2. Fan and stack,
  3. Transmissometer system, and
  J4. Control panel  and strip chart
     recorder.
  Table 1.2 lists the design and
 performance specifications for the
 smoke generator. It must generate
 smoke with an opacity range of 0 to
 100 percent and be sufficiently
 accurate  to allow the operator to
 control and stabilize the opacity  of the
 smoke. It is recommended that the
 generator also achieve and hold
 opacities in 5 percent increments at
 ±2 percent for a minimum of 5 s.
  White smoke is produced by
 dispensing, at regulated rates. No. 2
 fuel oil into the propane-heated
 vaporization chamber. The opacity
 varies in proportion to the volume of
 fuel oil vaporized and is regulated by
 adjusting the flow of fuel  oil.
  Black smoke is produced by the
 incomplete combustion of toluene in
the double-wall combustion chamber.
The toluene flowrate is also controlled
by valves and flowmeters.

1.2.5   Equipment Calibration
Procedures — Detailed calibration
procedures are included in a QA
procedures manual for VE training
programs.' The generator transmisso-
meters must be calibrated every six
months or after each repair. The
National Bureau of Standards (NBS)
traceable standards (optical filters) for
linearity response are available from
Quality Assurance Division,
Environmental Monitoring Systems
Laboratory, U.S. EPA, Research
Triangle Park, North Carolina 27711.
It is strongly recommended that the
calibration be performed before and
after each certification course to
ascertain whether any significant drift
or deviation has occurred during the
training period. The "zero and span"
check  must be repeated before and
after each test run. If the drift exceeds
1 percent opacity after a typical 30-
min test run, the instrument must be
corrected to 0 and 100 percent of
scale before resuming the testing.
  All of the smoke generator
performance verification procedures
(e.g., repair and maintenance work,
spectral response checks, calibration
check, and response time checks)
should be documented in writing and
dated; a bound logbook is highly
recommended. These records become
part of the permanent files on the VE
training program.

7.2.6  Setup, Operating, and
Shutdown Procedures — Detailed
procedures and a parts list are given
in Section 4.4 of Reference 1.

1.2.7  Storage and Maintenance of
the Smoke Generator — Proper
storage and maintenance procedures
are essential for smoke generators to
increase their useful operating life
and to provide reliability.
7.2.5  Common Problems, Hazards.
and Corrective Actions — The
generator has hot surfaces that can
cause serious burns. It is
Table 1.2.  Smoke Generator Design and Performance Specifications

        Parameter	  	Performance
Light source

Photocell spectral response

Angle of view
Angle of projection
Calibration error
Zero and span drift
Response  time	.
 Incandescent lamp operated at ±5% of
 nominal rated voltage
 Photopic (daylight spectral response
 of the human eye)
 15° maximum total angle
 15° maximum total angle
 ±3% opacity, maximum
 ±1% opacity, 30 min
 5 s, maximum
recommended that attendees be
advised to stay away from the
generator during training and test
runs. It is also recommended that gas
and fuel lines be correctly checked for
leaks prior to each use of the
generator to prevent fire and explosive
hazards to the operator and nearby
attendees.
  Occasional breakdowns or
malfunctions of the generator usually
occur at the most  inopportune times.
The problem must be diagnosed and
repairs made expedrtiously to provide
the proper training and maintain the
interest of the course  attendees.
Some common malfunctions are listed
in Section 4 of the QA training
manual.'
1.3   Certification of Observer
  This section summarizes the
certification part of the training
program. The first part of the
certification program is to acclimate
the smoke readers. The following
procedure is recommended. Both
black and white plumes are produced
at certain levels, and during this
production, the opacity values are
announced. After  some standards
exposure, four plumes are presented
to the trainee for evaluation. The
correct values of the four plumes are
announced to provide the trainee with
immediate feedback. The majority of
the trainees should be ready to take
the test after a few sets. Certification
runs are made in  blocks of 50
readings (25 black smoke and 25
white smoke). The trainees who
successfully meet the criteria receive
a letter of certification and a copy of
their qualification  form. The school
retains the original of the qualification
form for a minimum of three years, to
be available for any  legal proceedings
that might occur. According to Method
9, certification is valid for a period of
only six months. Neither certification
or recertification procedures require
the observer to attend the lecture
program; however, it is recommended
that the observer attend the series
during initial certification and
thereafter every three years. It is also
recommended that all persons unable
to pass after 10 qualification runs, be
provided additional training before
allowing qualification  runs to be
made.
  Test forms vary greatly because of
the specific needs and experiences of
each agency. Figure 1.1 illustrates
one suggested form. The form should
be printed on two-copy paper, the
original for the official file and the
carbon copy for the trainee to grade
after each certification run. The test
o
 o

-------
                              April 1983
                                                                                 Section 3.12.1
Affiliation 5TAT&
Course location
Date _ 4* -75- 83
                                                            . Sunglasses
                                                                           	_i_ Run Number  /~
                                                                           NO
. Sky.
                                                                                  'Wind
Distance and direction to stack
                                 FT. HrJ£.
Reading
number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25


0
0
0
O
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0


5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5


10
10
10
JO
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10


15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15


20
20
20
(gfo
20
20
20
.20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20


 30
GJ§)
30
30
Q§)
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30


35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35


40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40


45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45


50
50
@jy)
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50


55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55


60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60


65
65
65
65
65
65
65
65
65
65
65
65
65
65
65
65
65
65
65
65
65
65
65
65
65


70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
7O
70
70
70
70


75
75
75
75
75
75
75
75
75
75
75
75
75
75
75
75
75
75
75
75
75
75
75
75
75


80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80

•
85
85
85
85
85
85
85
85
85
85
85
85
85
85
85
85
85
85
85
85
85
85
85
85
85


90
9O
90
90
90
90
90
90
90
90
90
90
90
SO
SO
SO
SO
so
so
so
so
so
so
so
so


95
95
.95
95
95
95
95
95
95
95
95
95
95
95
95
95
95
95
95
95
95
95
95
95
95


100
100
100
100
100
100
1OO
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
                                                                                                                     Error
                                                                                                       Deviation.
Reading
number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25


0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
O
0
0
0
0
0


5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5


10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10


15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15


20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20


25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25


30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30


35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35


40
40
40
40
40
40
40
40
40
40
40
40
40
•40
40
40
40
40
40
40
40
40
40
40
40


45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45


50
50
50
50
50
SO
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50


55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55


60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60


65
65
65
65
65
65
65
65
65
65
65
65
65
65
65
65
65
65
65
65
65
65
65
65
65


70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70


75
75
75
75
75
75
75
75
75
75
75
75
75
75
75
75
75
75
75
75
75
75
75
75
75


80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80


85
85
85
85
85
85
85
85
85
85
85
85
85
85
85
85
85
85
85
85
85
as
85
85
85


90
90
90
9O
90
90
90
90
90
90
9O
90
90
9O
90
SO
SO
SO
SO
SO
SO
SO
SO
SO
SO


95
95
95
95
95
95
95
95
95
95
95
95
95
95
95
95
95
95
95
95
95
95
95
95
95


100
100
100
100
100
100
1OO
1OO
100
100
100
100
100
100
1OO
100
100
100
100
100
100
100
100
too
100
                                                                                                                     Error
                                                                                                       Deviation.
Figure 1.1.    Sample certification test form.

-------
                            April 1983
                                                                          Section 3.12.1
form must be filled in completely.
Certification requires that both of the
following criteria be satisfied:
  1. No reading may be in error by
     more than 15 percent opacity.
  2. The average [absolute] error
     must not exceed 7.5 percent for
     either set of 25 white or 25 black
     smoke readings. The certification
     runs may be repeated as  often as
     necessary. However, it is recom-
     mended that all persons who
     have not passed after ten certi-
     fication runs be given addi-
     tional training prior to conducting
     additional certification runs.
  The detailed testing and grading
procedures required to ensure a valid
test are outlined in Section 5 of the
QA training manual.1 The Agency
should maintain a  bound logbook,
arranged by training session, for at
least three years, as evidence that the
observer has been certified as a
qualified VE evaluator by a  recognized
smoke training and certification group.
Each trainee who successfully meets
the Method 9 criteria receives a letter
of certification and a copy of his/her
qualification form. This letter includes
the date of expiration.
1.4  Recertification
  Method 9 requires an individual to
be recertified every six months.
  2. The difference of the average
    value between observers shoulc
    not exceed 10 percent.

1.6  Smoke School
Certification Quality
Assurance Program
  It is recommended that any
government agency planning to
develop a smoke school certification
program obtain a copy of the
"Recommended Quality Assurance
Techniques and Procedures for Visible
Emission Training  Programs."1 Table
1.3 contains an activity matrix for
certification and training of observers.
o
                                                                               o
1.5  In-the-Field Training
  After the observer's initial
certification, it is recommended that a
senior observer accompany the new
observer on a field observation trip
and that both individuals
simultaneously record (using the
same time piece) their opacity
readings as a QA check (see Section
3.12.7). A comparison of these
readings will indicate any problems
the new observer might have in
conducting observations under field
conditions. A significant discrepancy
between the readings of the two
observers, in individual  or average
values, indicates the need for further
in-field training and continuance of
the senior observer (not necessarily
the same one) QA check. After
satisfactory checks have been made
on two consecutive field observations,
the new observer can confidently
conduct inspections without a senior
observer. The suggested standard for
a satisfactory check for 6-min
(minimum) of consecutive readings is:
   1. No difference in individual
     readings should exceed 20
     percent.
                                                                               O

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Section 3.12.1
April 1983
Table 1.3. Activity
Activity
Classroom
training of
observer
Smoke generator






Setup, operating.
and shutdown
procedures
Storage and
maintenance
Transmissometer
Design and perfor-
mance specifications



Calibration







Zero and span





Certification of
observer







Recertification





In-the-field training











Matrix for Certification and Training of Observers
Frequency and Action if
Acceptance method of requirements
limits measurement are not met
Classroom train-
ing per Ref. 1
(suggested)
Should be able
to generate
smoke with an
opacity range of
0 to 1OO%: hold
opacities ±2%
for at least 5 s
Adherence to
procedures in
Ref. 1
As above


Specifications in
Table 1.2



±3% opacity
maximum






Opacity drift
<1% after a
typical 30-min
test run


No reading must
be in error by
more than 15%
and average
absolute error
must not exceed
7.5% for either
white or black
smoke readings
As above





No reading in
error by more
than 20% differ-
ence and
average absolute
error should
not exceed
10% difference
during the field
observation


Initially and
every 3 years

Before each
certification test
run; use method
in Ref. 1



Each test run


As above


Upon receipt.
repair, and at
6-mo intervals
use method in
Ref. 1
Every 6 mo or
after repair.
before and after
'each certifica-
tion course is
recommended;
use method in
Ref. 1
As above





Take smoke
reading test until
a successful test
has been com-
pleted




Every 6 mo take
a smoke reading
test until a
successful test
has been
completed
Checks are made
on the first two
field observa-
tions subse-
quent to the
initial certifica-
tion; comparison
is made between
new certified
observer and an
experienced
observer
Review training
procedures per
Ref. 1
Adjust and make
repeat check of
operation




Review pro-
cedures

As above


Adjust and
repeat specifica-
tion check until
specifications
are met
Adjust and
recalibrate until
acceptance
limits are met




Instruments
must be cor-
rected to 0 and
10O% before
testing is
resumed
Retake test until
successful com-
pletion






As above





Continue com-
parisons until
acceptance
limits are met
during two field
observations






                                                                   I
                                                                           •

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o
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                           April 1983
                                   Section 3.12.2
                        2.0 Procurement of Apparatus and  Supplies
  Method 9 does not specifically
require any equipment or supplies.
Therefore/this entire section includes
quality assurance procedures that are
recommended to assist the observer
in documenting data. Nevertheless,
this section provides specifications
criteria or design features, as
applicable, to aid in the selection of
equipment that may be useful in
collecting VE data. Procedures and
limits for acceptance checks are also
provided. During the procurement of
equipment and supplies, it is
suggested that a procurement log
(Figure 2.1) be used to record the
descriptive title of the equipment, the
identification number (if applicable),
and results of any acceptance checks.
Table 2.1 at the end of this section
contains a summary of the quality
assurance activities for procurement
and acceptance of apparatus and
supplies.
2.1   Stopwatch
  A watch is used to time the 15-
second intervals between opacity
readings. The watch should provide a
continuous display of time to the
nearest second.
2.2  Compass
  A compass is useful for determining
the direction of the emission point
from the spot where the VE observer
stands and for determining the wind
direction at the source. For accurate
readings, the compass should be
magnetic wrth resolution better than
10°. It is suggested that the compass
be jewel-mounted and liquid-filled to
dampen the needle swing; map
reading  compasses are excellent for
this purpose.

2.3  Range Finder
  A range finder is used to measure
the observer's distance from the
emission point and should be capable
of determining distances to 1000
meters with an accuracy of ±10
percent. The accuracy of the range
finder should be checked upon receipt
and periodically thereafter with
targets at known distances of
approximately 500 meters and 1000
meters.
Item description
SfopwdfrcK


Quantity
z


Purchase
order
number
2-5076 '


Vendor
F/'sher
Scientific

Date
Ordered
5///3X


Received
5//y/s^


Cost
;52,?^


Disposition
checked-
reoiAy
J ,1 / K^o
TO t/OC_,.
Comments


•
Figure 2.1.    Example of a procurement log.

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                       Section 3.12.2
                                   April 1983
2.4  Abney Level or
Clineometer
  An Abney level is a device for
determining the vertical viewing angle.
For visible emission observation
purposes, it should measure within 5
degrees. The accuracy should be
tested by placing the level flat on a
table that has been previously leveled
with a referring level and checking it
at a 45° angle by placing it on a 45°
inclined plane constructed with the
plane as the hypotenuse of a right
triangle with equal base and height.

2.5  Sling Psychrometer
  The sling psychrometer is used in
cases where it is suspected that the
atmospheric conditions will promote
the formation of a steam plume (see
Subsection 6.3). The psychrometer
should consist of two thermometers,
accurate to 1/2°C, mounted on a
sturdy assembly whereby the
thermometers may be swung rapidly
in the air. One thermometer should be
fitted with a wettable cotton wick tube
on the  bulb. Thermometer accuracy
should be checked by placing the
bulbs in a fresh ice water bath at 0°C.

2.6   Binoculars
   It is recommended that the observer
obtain binoculars preferably with a
magnification of at least 8 x 50 or  10
x 50. The binoculars should have
color-corrected coated lenses and a
rectilinear field of view. Color
correction can be checked by viewing
a black and white pattern such as a
Ringelmann card at a distance greater
than 50 ft; no color rings  or bands
should be evident, only black and
white. The rectilinear field of view can
be tested by viewing a brick wall at a
distance greater than 50 ft. There
should be no distortion of the brick
pattern as the field of view is
changed. The binoculars are helpful
for identifying stacks, searching the
area for emissions and aid in
characterizing behavior and
composition of plume.

2.7   Camera and Accessories
   A camera is often used in VE
observations to document the
emissions before and after the actual
opacity determination. A 35-mm
camera with through-the-lens light
metering is recommended for this
purpose. Useful accessories include a
"macro" lens or a 250-mm to 350-
mm telephoto lens, and a 6-diopter
closeup lens (for photographing
logbook and evidence of particulate
deposition). A photo logbook is
necessary for proper documentation.
and the observer should always be
sure to purchase enough fresh color
negative film (ASA 100
recommended) for his/her purposes.

2.8   Clipboard and
Accessories
  For documenting the visible
emission observation, the observer
should have a 10 in. x 12  in. masonite
or metal clipboard, several black ball-
point pens (medium point), a large
rubber band, and a sufficient number
of visible emission observation forms.
2.9  Safety Equipment
  The following safety equipmem.
which should be approved by the
Occupational Safety and Health
Association (OSHA), is recommended
for the VE observer:
  O Hard hat in high-visibility yellow
    or orange
  O Safety glasses, goggles, or eye
    shields
  O Ear protectors
  O Safety shoes (steel-toed for
    general  industrial use).
Specially insulated safety shoes are
necessary in certain areas, such as
the top of coke ovens.
O
Table 2.1.     Activity Matrix for Procurement of Recommended Equipment and
            Supplies
Equipment
Watch '

Compass

Range finder






Abney level

Sling psychrometer



Binoculars





Camera



Clipboard/
accessories/forms



Safety equipment




Acceptance limits
Continuous
display
Magnetic with
10° resolution
Accuracy of
±1O% over dis-
tances to 1000m




Accurate within
±5°
Each thermom-
eter accurate
to 1/2°C (1°FJ

Magnification of
8x50 or 10x50,
color-corrected
coated lenses
and a rectilinear
field of view
35-mm camera
with through-
the-lens light
metering
10 in. by 12 in.
clipboard; black
ball-point pens;
VE observation
forms
Hardhat— yellow
or orange, safety
glasses and
shoes, ear
protectors
Frequency and
method of
measurement
Check upon
receipt
Check upon
receipt
Check upon
receipt and
quarterly with
targets at known
distances of
about 500m and
1000m
Check at 0° and
45°
Check thermom-
eter accuracy
with ice water
bath at 0°C
Check upon
receipt by view-
ing selected
objects


Check quality of
photos on
receipt and after
processing film
Check supplies
periodically



Check supply of
safety equip-
ment periodi-
cally

Action if
requirements
are not met
Return to
supplier
Return to
supplier
Adjust or
return to
supplier




Same as above

Repair or return
to supplier


Return to
supplier




Return to
supplier lor
repair

Replenish
supplies



Maintain equip-
ment availability



                                                                           O
                                                                            O

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                            April 1983
                                     Section 3.12.3
                                  3.0   Preobservation Operations
  The following procedures are not
required by Method 9 but are
recommended in order to provide
more consistent data collection and
better data documentation and
verification of representative plume
viewing conditions. Not all procedures
are needed for  every observation.
  Before making on-site VE
determinations, the observer should
gather the necessary facility data,
provide prior notifications when
applicable, establish an observation
protocol, and check for availability of
supplies and property maintained
equipment. Table 3.1 at the end of
this section summarizes the quality
assurance activities for preobservation
operations.

3.1  Gather Facility
Information
  The observer  should be thoroughly
familiar with the source facility,
operation, emissions, and applicable
regulations. In preparation for the on-
site visit, the observer should review
the Agency's information (in the official
source file) on the source in question.
The observer should:
    1. Determine the pertinent people
      to be contacted.
    2. Become familiar with the
      processes and operations at the
      facility and identify those
      facilities to be observed.
   3. Review the  permit conditions,
      requirements, and recent
      applications.
   4. Determine applicable emission
      regulations.
   5. Identify all operating air
      pollution  control equipment,
      emission points, and types and
      quantities of emissions.
   6. Review history of previous
      inspections, source test results,
      and complaints.
   7. Check the file to become
      familiar with (or review) plant
      layout and possible observation
      sites.
   8. Determine normal production
      and operation rates.
   9. Identify  unique problems  and
      conditions that may be
      encountered (e.g., steam
      plume).
  10. Discuss with attorney if case
      development is expected.
  11. Obtain a  copy of the facility
      map with labeled emission
      points, profile drawings, and
      photographs, if available. A
      facility map is very helpful
      during inspection and should be
      a required item for every
      Agency source file. The map
      makes it easier for the observer
      to identify point sources and
      activities, and it may be used to
      mark any emission points that
      have been added or modified.
   12. If  an operating permit  exists,
      obtain a copy because it may
      contain the VE limits for each
      point source and any special
      operating requirements.
   13. Determine the status of the
      source with respect to any
      variance or exemption from the
      Agency's  rules and regulations.
      Observation may not berequired if
      the source has a variance or is
      exempt from the regulations.
   14. Review plant terminology.
   15. Use references such as facility
    ,  maps and previous inspection
      reports to determine if the
      viewing position is restricted
      because of buildings or natural
      barriers. If the viewing position
      requires observations to be
      taken at a particular time of day
      (morning or evening) because
      of sun angle, consider this
      when planning the inspection.
   16. Determine the possibility of
      water vapor in the plume
      condensing (see Section
      3.12.6). This determination may
      prevent a wasted trip to the
      facility on days when a
      persistent water droplet plume
      is anticipated because of
      adverse ambient conditions.
Note: If the observer is not familiar
with the type of facility or  operation,
he/she should consult available
reference material and inspection
manuals on the  source category.

3.2  Prior Notification
  The-usual procedure is to make the
VE determination without prior
notification unless the plant  must be
entered first to obtain a good view of
the emission point of interest.
However, this procedure is not always
possible, especially in remote
locations, when  operations are
intermittent, or when  specific
personnel must be present or
contacted. Determining VE for
compliance with State Implementation
Plan (SIP) or NSPS opacity regulations
 requires on-site observations during
 conditions of typical or normal
 maximum operations. If the facility is
 notified of the time of this evaluation,
 some operating conditions  may be
 altered, ft this situation appears likely,
 it is EPA's policy not to give prior
 notification. EPA is obligated to notify
 State/local agencies of inspections
 and generally prefers to invite the
 applicable agency to participate. The
 observer should notify  the affected
 facility and control agencie? as soon
 as practical following any official
 opacity readings.

 3.3  Establish Observation
 Protocol
   Based on information collected
 under'-Section 3.1  and any prior
 experience with the source, an
 observation protocol should be
 established. First, the observer
 should determine whether one, two,
 or more observers will be required.
 For  example, two observers may be
 required to simultaneously make the
 VE determination and gather other
 on-site data (e.g., take photographs,
 draw a new modified facility map if
 one is not available from the plant or
 gather other needed plant information).
 In certain situations where the VE
 observations must be correlated to
 process operation, the  second person
 will closely monitor the process
 activity and record the exact time of
 the  operating modes of interest Only
 one observer will make the VE
 determination unless an observer
 audit is being conducted. In this case,
 the  designated observer is the one
 being audited.
   The applicability of Method 9 (and
 hence the method of observation)
 should be determined.  If Method 9 is
 not  applicable, see Section 3.12.4,
 Special Problems.
   A written checklist regarding an
 expected walk-through of the plant
 including questions to  ask plant
 officials may be helpful.

3.4  Perform Equipment
Checks for On-Site Use
  Be sure that the necessary
equipment and supplies are available
for making the VE determination and
documenting the results. All
equipment should be visually checked
for damage and satisfactory operation
before each VE determination field
trip.

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Section 3.12.3
                                                  April 1983
TableS. 1 . Activity Matrix for Preobservation Operations
Frequency and
Acceptance method of
Activity limits measurement
Gather facility
information


Make prior
notification








Establish protocol


Perform equipment
check



Obtain neces-
sary facility data.
Subsec 3. 1

Make VE deter-
mination with-
out prior notifi-
cation except as
stated in Subsec
3.2; EPA should
notify State/
local agencies
and invite
participation
Prepare obser-
vation protocol.
Subsec 3.3
All equipment/
supplies avail-
able and in sat-
isfactory work-
inq order
Check for com-
pleteness of data


Check the pro-
tocol for notifi-
cation before
each on-site visit
and revise the
protocol as
necessary



Check before
on-site visit

Same as above




Action if
requirements
are not met
Obtain missing
data before on-
site visit, if
possible
Make required
notifications








Complete or
prepare protocol
as required
Replace or
adjust
equipment


                                                                                           o
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                            April 1983
                                    Section 3.12.4
                                  4.0   On-Site Field Observations
  This section describes field
observation procedures, including
perimeter survey, plant entry, VE
determination, and special observation
problems. The latter subsection
supplements the subsection on VE
determination by providing some
information on how to take VE
readings when unfavorable field
conditions prevent the use of the
procedure described in Subsection 4.3
(e.g., when the emissions are
intermittent or the observer position is
restricted). The QA activities are
summarized in Table 4.2 at the end of
this section.

4.1   Perimeter Survey
  Before and  after the VE
determination, it is strongly
recommended that the observer make
a perimeter survey of the area
surrounding (1) the point of
observation and (2) the emission point
on which the determination is being
made. Such a survey also may be
made during the VE determination, if
warranted.
  A perimeter survey can be useful
in determining the presence of other
factors that could affect the  opacity
readings. For  example, the
representativeness of the VE readings
for a given emission point could be
questioned unless data is available to
show that the observer excluded
emissions related to material
stockpiling, open burning, and
ambient condensed water vapor in
adjoining areas of the plant. It is vital
that the observer be as aware as
much as possible of extenuating
conditions. The perimeter survey is
made to document these conditions.
Common sense should be used in
determining the need and extent of
the survey; in  some cases (e.g., a
single 350-foot stack) a perimeter
survey is not vital.
  Perimeter surveys can be  made
from either outside or inside the plant
property, or both. This decision would
depend on whether the VE
observations are made from inside or
outside of the plant, whether the
observer actually gains entry to the
plant  premises, and whether the plant
is sufficiently visible from outside the
premises to make a reasonable
survey. It is suggested that during  the
survey the observer should note such
factors as:
  1.  Other stacks and emission points
     whose visible emissions might
     interfere with opacity readings.
  2.  Fugitive emissions that result
     from product or waste storage
     piles and material handling and
     may interfere with observations.
  3.  Fugitive emissions that result
     from unpaved road travel and
     may interfere with observations.
  4.  Water vapor emissions from
     sludge or cooling ponds.
  5.  Open burning.
  6.  Any unusual activities on or
     around plant premises that could
     result in nonrepresentative
     emissions or interfere with
     opacity readings.
  If deemed useful by the observer,
photographs may be taken to
document extenuating conditions (see
discussion of confidentiality and the
use of cameras in Subsection 4.2.7).

4.2  Plant  Entry
  The following discussion presents
the recommended plant entry
procedures. The VE readings
themselves should not be affected by
a change in these procedures.
However, the usefulness  of the
readings in showing a possible
violation of the applicable standards
may be compromised by not following
agency procedures for entering plants.
Depending on the location of emission
points at the plant and the availability
of observation points in the area
surrounding a facility, the VE observer
may not have to gain entry to the
plant premises prior to making VE
observations. It may be preferable to
gain access after taking readings to
check on plant process control
equipment operating conditions or to
complete a perimeter survey. Figure
4.1  is an example entry checklist that
can be used to assist the observer in
organizing the information that could
be used at the time of plant entry.
  To maintain a  good working
relationship with plant officials and,
most importantly, to comply with the
Clean Air Act and avoid any legal
conflict with trespass  laws or the
company's right to privacy and due
process of law under the U.S.
Constitution, the observer must follow
certain procedures in gaining entry to
the plant's private premises. In  most
cases, consent to enter (or the
absence of express denial to enter) is
granted by the owner or company
official. Figure 4.1 lists the pertinent
section of the Clean Air Act on facility
entry as well as information on
confidentiality of process information.
It is recommended that the inspector
have a copy of this information
available in case questions are raised
by source representatives.
4.2.1  Entry Point — It  is
recommended that the plant premises
be entered through the main gate or
through the entrance designated by
the company officials in response to
prior notification. The observer's
arrival will usually occur during
normal working hours unless
conditions contributing to excess
opacity levels are noted  at certain
times other than normal working
hours. If only a guard is present at the
entrance, it  is desirable for the
observer to present the appropriate
credentials and to suggest that the
guard's supervisor be contacted for
the name of a responsible company
official. The observer would then ask
to speak with this official, who may be
the owner, operator, or agent in
charge (including the environmental
engineer).
4.2.2  Credentials — After
courteously introducing
himself/herself to the company
official, the observer should briefly
describe the purpose of the visit and
present the appropriate credentials
confirming that he/she is a lawful
representative of the agency. Such
credentials will naturally differ
depending upon  the agency
represented, but it is recommended
that they include at least the
observer's photograph, signature,
physical  description (age, height
weight, color of hair and eyes), and
the authority for  plant entry. Agencies
issue credentials in several forms.
including letters, badges, ID cards, or
folding wallets.

4.2.3  Purpose  of Visit — When first
meeting with a company official, the
observer needs to be prepared to state
succinctly the purpose of the visit
including the reason for the VE
determination. Space is provided in
the recommended form (Figure 4.1) to
specify the exact purpose of the visit,
and the observer can refer to this
when talking with the company
official.

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                     Section 3.12.4
                                                               April 1983
                                                                                                 lo
Source name and address
             E..QF
Observer  JuDY A. "5A1/77/

Agency
                                                               IT.
                                               Date of VE observation
Previous company contact (if applicable)
  Title
                                                 C-
  Purpose of visit  £/>/(  ^ub(T  M3f&ZT'6tf AND  VE.  O33&LWCT/O*)
     OFFICE  w$Pa<=r5  /O%OF rtr\jt>& sources  //V
  Emission points at which VE observations to be conducted
                                  X    c?3  OS
                                  3-0^-007-0^
  Authority for entry (see reverse side)
Plant safety requirements

El Hardhat
H Safety glasses
Ef S/tfe shields (on glasses)
D Goggles
D Hearing protection eM.Wrfc
  Specify
                                                 D Coveralls
                                                 f3 Dust mask suggested
                                                 D Respirators)
                                                    Specify	
                                PUA/T
    Safety shoes (steel-toed)
  O Insulated shoes
  O Gloves
                                                  Specify.
                                                    O
Company official contacted (on this visit)
                                                  O.
Figure 4.1.    Visible emission observer's plant entry checklist.
                                                                                                    O

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                            April 1983
                                     Section 3.12.4
Authority for Plant Entry: Clean Air Act, Section 114

(a)(2)  the Administrator or his authorized representative upon presentation of his credentials -

       (A)  shall have a right of entry to, upon or through any premises of such person or in which any records required to be
           maintained under paragraph (1) of this section are located, and
       (B)  may at reasonable times have access to, and copy of any records, inspect any monitoring equipment or methods
           required under paragraph (1), and sample any emissions which  such person is required to sample under
           paragraph (1).
(b) (1)  Each State may develop and submit to the Administrator a procedure for carrying out this section in such State. If the'
Administrator finds the State procedure is adequate, he may delegate to such State any authority he has to carry out this
section.
   (2)  Nothing in this subsection shall prohibit the Administrator from carrying out this section in a State.
(c)Any records, reports or information obtained under subsection (a) shall be available to the public except that upon a showing
satisfactory to the Administrator by any person that records, reports, or information, or particular part thereof, (other than
emission data) to which the Administrator has access under this section if made public would divulge methods or processes
entitled to protection as trade secrets of such person, the Administrator shall consider such record, report, or information or
particular portion thereof confidential in accordance with the purposes of Section 1905 of Title 18 of the United States
concerned  with carrying out this Act or when relevant in any proceeding under this Act."
Confidential Information: Clean Air Act, Section 114 (see above) 41 Federal Register 36902, September 1, 1976
  If you believe that any of the information required to be submitted pursuant to this request is entitled to be treated as
confidential, you may assert a claim of business confidentiality, covering all or any part of the information, by placing on (or
attaching to) the information a cover sheet, stamped or typed legend, or other suitable notice, employing language such as
"trade secret," "proprietary." or "company confidential." Allegedly confidential portions of otherwise nonconfidential
information should be clearly identified.  If you desire confidential treatment only until the occurrence of a certain event; the
notice should so state. Information so covered by a claim will be disclosed by EPA only to the extent, and through the procedures,
set forth at 40 CFR, Part 2, Subpart B (41 Federal Register 36902, September  1, 1976.)

  If no confidentiality claim accompanies this information when it is received by EPA, it may be made available to the public by
EPA without further notice to you.
Figure 4.1.    Reverse side of form. (Continued)
  The principal purpose for an
observer's visit to a plant will probably
fall into one of three categories: (1) a
VE determination is being made
pursuant to a neutral administrative
scheme* to verify compliance with an
applicable SIP or NSPS, (2) a VE
determination is being made because
some evidence of an opacity violation
already exists, or (3) an unscheduled
VE determination has just been made
from an area off the plant property.
The statement of purpose should state
clearly what has prompted the visit.
  At this time, the observer also
should provide the company official
with a  copy of the opacity readings
and ask that person to sign an
acknowledgment of receipt of any VE
readings made previous to entry. In
lieu of  the above, the agency should
provide a copy within a reasonable
time.

4.2.4  Visitor's Agreements, Release
of Liability (Waivers) — The observer
should not  sign a visitor's agreement,
release of liability (waiver), hold-
harmless agreement, or any other
agreement that purports to release
•Any routine of selecting sites for observation
that is not directed toward any company.
the company from tort liability.
Signing this type of release form may
waive the rights of the observer and
his/her employer compensation in
event of personal injury or damages;
the precise effect of signing an
advance release of liability for
negligence depends upon the laws of
the state in which it is signed. If the
plant official denies entry for refusal
to sign a release form, the observer
should proceed as described in the
section on entry refusal.

4.2.5  Section 114 — Section 114 of
the Clean Air Act addresses both the
authority for plant entry and the
protection of trade secrets and
confidential information. For the
observer's reference, the applicable
paragraphs are included on the
reverse side of the entry checklist in
Figure 4.1.
4.2.6  Entry Refusal — In the event
that an observer is refused entry by a
plant official or that consent is
withdrawn before the agreed-upon
activities have been completed, the
following procedural steps should be
followed:
  1. Tactfully discuss the reason(s) for
     denial with the plant official; this
     is to insure that the denial
     has not been based on some sort
     of misunderstanding. Discussion
     might lead to resolution of the
     problem and the observer may be
     given consent to enter the
     premises, rf resolution is beyond
     his/her authority, the observer
     should withdraw from the
     premises and contact his/her
     supervisor to decide on a
     subsequent course of action.
   2. Note the facility name and exact
     address, the name and title of
     the plant officials approached,
     the authority of the person
     issuing the denial, the date and
     time of denial, the reason for
     denial, the appearance of the
     facility, and any reasonable
     suspicions as to why entry was
     refused.
   3. The observer should be very
     careful  to avoid any situations
     that might be construed as
     threatening or inflammatory.
     Under no circumstances should
     the potential penalties of entry
     denial be  cited.

All evidence obtained prior to the
withdrawal of consent is considered
admissible in court.
                                                                                            f

-------
                         Section 3.12.4
                                     April 1983
  When denied access only to certain
parts of the plant, the observer should
make note of the area(s) and the
official's reason for denial. After
completing normal activities to the
extent possible and leaving the
facility, the observer should contact
his/her supervisor for further
instructions.

4.2.7  Confidentiality of Data — In
conducting the VE investigation, the
observer may occasionally obtain
proprietary or confidential business
data. It is essential that this
information be handled properly.
  The subject of confidential business
information known as  "a trade secret"
is addressed in Section 114 of the
Clean Air Act (see Subsection 4.2.5)
and in the Code of Federal
Regulations (40 CFR 2; 41 Federal
Register 36902, September 1, 1976,
as amended). The Code of Federal
Regulations (40 CFR 2, Subpart  B,
2.203) embodies a notice to be
included in EPA information requests.
This notice is paraphrased on  the
reverse side of the entry checklist
(Figure 4.1) for the observer's and
plant official's reference. The Code of
Federal Regulations (40 CFR 2.
Subpart B,  2.211) also includes the
penalties for wrongful disclosure of
confidential information by Federal
employees, in addition to the penalties
set forth in the United States Code,
Title 18, Section 1905. Employees of
other agencies should check with
agency attorneys to determine their
exact personal liability.
  From the observer's standpoint,
confidential information may be
defined as information received under
a request  of confidentiality which may
concern or relate to trade secrets. A
trade secret is interpreted as an
unpatented secret, commercially
valuable plan, appliance, formula, or
process used in production. This
information can be in written  form, in
photographs, or in the observer's
memory. Emissions data are not
considered confidential information.
Also the Agency reserves the right to
determine if information submitted to
it under an official request should be
treated as confidential.
  A good  rule of thumb for the
observer to follow is to collect only
that process and operational
information and to take only those
photographs that are pertinent to the
purpose of the plant visit. The plant
official should be advised that he
must request confidential treatment of
specific information provided (see
paragraph on claims of confidentiality
on reverse side of entry checklist)
before it will be treated as confidential
pending legal determination. The plant
official should inform the observer of
any sensitive areas of the facility or
processes where proprietary or trade
secret information is indicated.
  Photographs are often used to
document visible emissions
observations (see Subsection 4.3.4).
Before taking photographs from inside
the plant premises, the observer must
have the consent of the plant official.
Most of an observer's photographs
will be of emission points only;
presumably, these should not include
confidential areas of the plant. If any
opposition is encountered regarding
the use of a camera  on the plant
premises,  the observer should explain
that the plant official should request
confidential treatment of  any
photographs taken. The observer
must properly document each
photograph and handle those for
which confidential treatment has been
requested in the same manner as
other  confidential data. Photographic
documentation of VE observations
from an area of public access outside
of the plant premises does not require
approval from a plant official, provided
the documentation is accomplished
without the use of highly
sophisticated equipment or
techniques. For example, use of a
high-power telephoto lens (over 100
mm on a 35 mm camera) that yields
extensive details (e.g., construction
layout) might be construed as
surreptitiously taking confidential
business information. Thus, a good
rule of thumb is to be sure that any
pictures taken show only the details
that could be seen with the naked eye
from an area accessible to the public.
  When preparing to leave the plant,
the observer should allow the plant
official to  examine the data collected
and make claims of confidentiality. All
potentially confidential information
should be so marked, and while on
the road, the observer should keep it
in a locked briefcase or file container.
It should be noted that emission data
are not considered confidential.
  When the observer returns to the
agency office, the potentially
confidential information should be
placed in a secure, lockable file
cabinet designated especially for that
purpose. The observer's agency
should have an established secure
filing  system and procedures for
safeguarding confidential documents.
In all  cases, the observer should make
no disclosure of potentially
confidential information until a
company has had full opportunity to
declare its intentions regarding the
information and the Agency has ruled
that the information is not legally
confidential.

4.2.8  Determination of Safety
Requirements — The violation of a
safety  rule does not invalidate VE
readings; however, the observer
should always anticipate safety
requirements by arriving at the plant
with a hardhat, steel-toed safety
shoes, safety glasses with side
shields, and ear protectors. Safety
equipment also should include any
other equipment that is specified in
the agency files and noted on the
entry checklist form.

  Some companies require unusual
safety equipment, such as specific
respirators for a particular kind of
toxic gas. In many cases, these
companies will provide the observer
with the necessary equipment. In any
event, the observer must be aware of
and adhere to all safety requirements
before entering the plant. Information
on plant alarms and availability of first
aid and medical help may be needed.
4.2.9  Observer Behavior —
Observers must perform their duties
in a professional, businesslike, and
responsible manner. They should
always consider the public relations
liaison part of their role by seeking to
develop or improve a good working
relationship with plant officials
through use of diplomacy, tact, and rf
necessary, gentle persuasion in all
dealings with plant personnel.

   Specifically, observers should be
objective  and impartial in conducting
observations and interviews with
plant officials. All information
acquired during a plant visit is
intended  for official use only and
should never be used for private gain.
Observers must be careful never to
speak of any person, agency, or
facility in any manner that could be
construed as derogatory. Lastly,
observers should use discretion when
asked to give a professional opinion
on specific products or projects and
should never make judgments or draw
conclusions concerning a company's
compliance with applicable
regulations. Upon giving the data to
the plant the observer can tell the
source these are the data that were
obtained  and no judgment as to
compliance can be made until all the
data and  the regulations are closely
reviewed.
o
 o
 o
                                                                                     •'/
-------
                             April 1983
                                    Section 3.12.4
  4.3   Visible Emission
  Detormination
    This subsection describes the
  preferred approach to VE
  determination. Because practical
  considerations do not always permit
  the observer to follow this procedure,
  however, special observation
  problems are discussed in Subsection
  4.4.

  4.3.1   Opacity Readings —  The
  observer must be certified in
 "accordanee^vith Section 3.12.1,
  SubsectioVi 1.3, and should use the
  following procedure for visually
  determining the opacity of emissions.
  Observer Position
    1. The observer must stand at a
      distance that provides a clear
      view of the emissions with the
      sun oriented in the 140° sector
      to his/her back. If the observer
      faces the emission/viewing point
      and places the point of  a pencil
      on the sun location line such
      that the shadow crosses the
      observers position, the sun
      location (pencil) must be within
      the 140° sector of the line.
      During overcast weather
      conditions, the position  of the
      sun is less important.
   2. Consistent with number 1 above,
      when possible, the observer
      should, make observations from
      a position in which the  line of
      vision is approximately
      perpendicular to the plume
      direction; when observing
      opacity of emissions from
      rectangular outlets (e.g., roof
      monitors, open baghouses, and
      noncircutar stacks), the
      observer's position should be
      approximately perpendicular to
      the longer axis of the outlet.
    3. When multiple stacks are
      involved, the observer's line of
-.,', \ '.sight should not include more
    ''••  than one plume at a time,  and in
      any case, during observations,
      the observer's line of sight
      should be perpendicular to the
      longer axis of a set of multiple
      stacks (e.g., stub stacks on
      baghouses).
    4. The observer must stand at a
      distance that provides total
      perspective and a good view.
    5. In order to comply with the sun
      angle requirements (see item 1)
      it is recommended that the
      observer should try to avoid the
      •noon hours (11:00 a.m. to 1:00
      p.m.) in the summertime (when
      the sun is almost overhead). This
      is more critical in the southern
     continental United States. The
     preferred reading distance is
     between 3 stack heights and 1/4
     mile from the base of the stack.

  6. The reading location should be
     safe for the observer.

Opacity Observations
  1. Opacity-observations must be
     made at the point of greatest
     opacity in that portion of the
     plume where condensed water
     vapor is not present.
  2. The observer must not look
     continuously at the plume (this
     causes eye fatigue), but should
     observe the plume momentarily  >"-
     at 15-s intervals. A 15-s beeper
  '-  is recommended to aid in
.-.,':  performing the VE readings.
  3. When steam plumes are
     attached,  i.e., when condensed
     water vapor is present within the
     plume as  it emerges from the
     emission outlet, the opacity must
     be evaluated beyond the point in
     the plume at which condensed
     water vapor is no longer visible.
     The observer must record the
   , approximate distance from the
     emission outlet to the point in
     the plume at which the
     observations are made.
  4. When steam plumes are
     detached, i.e., when water vapor
     in the plume condenses and
     becomes visible at a distinct
     distance from the emission
     outlet, the opacity of emissions
     should be evaluated near the
     outlet, prior to the condensation
     of water vapor and the formation
     of the steam plume, unless the  -
     opacity is higher after
     dissipation.
  5. Readings  must be made to the
     nearest 5 percent opacity. A
     minimum of 24 observations
     must be recorded. It is advisable
     to read the plume for a
     reasonable period in excess of
     the time stipulated in the
     regulations (i.e., at least 10
     readings more than the minimum
     required).
  6. A clearly visible background of
     contrasting color'is best for
     greatest reading accuracy.
     However, the probability of
     positive error (higher values) is
     greater under these conditions.
   . Generally, the apparent plume
     opacity diminishes and tends to
     assume a negative bias as the
     background becomes less
     contrasting.
  7. It is recommended the observer
     wear the same corrective lenses
    that were worn for certification.
    If sunglasses were not worn
    during certification, the observer
    should remove them and allow
    time for the eyes to adjust to the
    daylight before making VE
    determinations. It'is
    recommended that the observer
    not wear photo compensating
    sunglasses.
  8. The best viewing spot is usually
    within one stack diameter above
    the'stack exit, where the plume
    is densest and the plume width
   " is approximately equal to  the
    stack's diameter.

4.3.2  Field Data: The  "Visible
Emission Observation Form" — The
1977 revision of EPA Method 9
specifies the recording of certain
information in the field documentation
of a visible emission observation. The
required information includes the
name of the plant, the emission
location, the type of facility,  the
observer's name and affiliation, the
date, the time, the estimated distance
to the emission location, the
approximate wind direction, the
estimated windspeed, a description of
the sky conditions (presence and color
of clouds), and the plume background.
  Experience gained from past
enforcement litigation involving
opacity readings as primary evidence
of emission standards violations has
demonstrated a need for additional
documentation when making visual
determinations of plume opacity. The
Visible Emission Observation Form
presented in Figure 4.2 is
recommended. This form was
developed after reviewing the opacity
forms used in EPA Regional Offices
and State and local air  quality control
agencies, the form includes not only
the data required by Method 9. but
also the information necessary for
maximum legal acceptability. Valid
data can be collected on any form;
however, the recommended form may
enhance observer efficiency and data
documentation. A detailed description
of the use of the recommended form
is given in the following paragraphs.

  The Visible Emission Observation
Form can bo functionally divided into
11 major sections, as .shown in Figure
4.3. Each section documents one or
two aspects of the opacity
determination. The form endeavors to
cover all the required and
recommended areas of documentation
in a typical opacity observation. A
"comments" section is included for
notation of any relevant information
that is not listed on the form.

-------
                      Section 3.12.4
                                            April 1003
                                                                                              o
             VISIBLE EMISSION OBSERVA TION FORM
  SOURCE NAME
  ADM WV.
                            OBSERVATION DATE
                             15 JULY mi.
                                                                            STOP TIME
 ADDRESS
  //a. OCEAN WAD
                                        15
                                                          30
                                                       45
                    15
                    30
45
                                                       30
                                       35
                                                         53
                                                      55
          31
           CTtr
 wo/wr
           -5/0/
                                                      55
                                       30
                                                              30
                                                            32
     SOURCE ID NUMBER
                                                       35
                                       25
                                                         35
                                                      35
                                                                          33
                                  30
                                                     35
                                                           34
 PROCESS EQUIPMENT -
 CONTROL E QUIPMENT
           O/»f /M 7WG M ODE
                                                       30
                                       3D
                                                         30
                                                      30
                                                     35
           OPERATING MODE
                                                35
                                             35
35
35
                                                                          36
 DESCRIBE EMISSION POINT, „,

                    *
                                                       30
                                       30
                                                          35
                                                      35
          37
                                                       35
                                                55
                                                                    38
 HEIGHT ABOVE GROUND LEVEL
 START flX> '   STOP iX
 DISTANCE fROM OBSERVER

 START 4&*   STOP •"*"
    HEIGHT RELATIVE TOOBSERVEfi
    START A>O'  STOP*/'
                                                60
                                                 55
          39
     DIRECTION FROM OBSERVER
     START MA/E.  SrCV»,X
                                                  10
                                           35
                                                              30
                                                            40
                                            11
                                        30
     SO
      41
 DESCRIBE EMISSIONS .
 START t*PTt*Utf***e.
   STOP
                              12
                                                30
                                                30
                                                            42
 STA
fop  S
     PLUME TYPE: CONTINUOUS*?
    fucmvEO
                                                  13
                                                      43
                                                  14
                                                                    44
 WATER DROPLETS PRESENT:
     IF WATER DROPLET PLUME:
     ATTACHED^ DETACHEDO
                                                  15
                                                                    45
 POINT IN THE PLUME A T WHICH OPA CITY WAS DETERMINED
 START 0'
                                                  16
                                                      4S
                              17
                                                                    47
                                                                                  O
 DESCRIBE BACKGROUND
 START
                              18
                                                                    43
 BACKGROUND COLOR
 START BUK   STOPCa%~ff
    SKY CONDITIONS
    START O&&. STOP
                                                  19
                                                      49
                                           20
                                                            SO
 WIND SPEED

 START
    WIND DIRECTION
    START  SlJ   STOP
                                            21
                                                            SI
 AMBIENT TEMP.
 START ^5V  STOP
    WET BULB TEMP.  RH.percen
                                                  22
                                                      52
                             23
                                                                    63
                                                  24
                                                      S4
 Sourco Layout Sketch     Draw North Arrow
rni  i u  11 maa
                                                  25
                                                      55
                                                  26
                                                      66
                 .......


                 /
                 '
 K)£m'uit
                         mistion Point
                                                  27
                                                      57
 Si/n-<^ Wi>
   Plume end 
-------
                               April 1983
                 Section 3.12.4
                                           VISIBLE EMISSION OBSERVA TIONFORM

 This form is designed to be used in conjunction with EPA Method 9, "Visual Determination of the Opacity of Emissions from Stationary
 Sources." Any deviations, unusual conditions, circumstances, difficulties, etc., not dealt with elsewhere on the form should be fully noted
 in the section provided for comments. Following are brief descriptions of the type of information that needs to be entered on the form; for a
 more detailed discussion of each part of the form, refer to the "User's Guide to the Visible Emission Observation Form."
 'Source Name - full company name, parent company or division
 information, if necessary.
 'Sky Conditions • indicate cloud cover by percentage  or by
 description (clear, scattered, broken, overcast, and color of clouds).
"Address - street (not mailing) address or physical location
of facility where VE observation is being made.

Phone - self-explanatory.
Source ID Number - number from NEDS. CDS. agency file, etc.

"Process Equipment. Operating Mode - brief description of process
equipment (include ID no.) and operating rate. % capacity utilization,
and/or mode (e.g., charging, tapping).

"Control Equipment. Operating Mode - specify control device type(s)
and % utilization, control efficiency.

"Describe Emission Point • stack or emission point location, geometry,
diameter, color; for identification purposes.
"Height Above Ground Level - stack or emission point height, from
files or engineering drawings.
 "Height Relative to Observer - indicate vertical position of observation
 point relative to stack top.


 "Distance From Observer - distance to stack ±10%; to determine, use
rangefinder or map.

 "Direction From Observer - direction to stack; use compass or map;
 be accurate to eight points of compass.

 "Describe Emissions - include plume behavior and other physical
 characteristics (e.g., looping, lacy, condensing, fumigating, secondary
particle formation, distance plume visible, etc.).

 "Emission Color - gray, brown, white, red, black, etc.
 Plume Type:
  Continuous - opacity cycle >6 minutes
  Fugitive - no specifically designed outlet
  Intermittent - opacity cycle <6 minutes

 * " Water Droplets Present • determine by observation or use wet sling
psychrometer; water droplet plumes are very white, opaque, and
billowy in appearance, and usually dissipate rapidly.

 ""If Water Droplet Plume:
  Attached - forms prior to exiting stack
  Detached - forms after exiting stack

 ""Point in the Plume at Which Opacity was Determined - .describe
physical location in plume where readings were rmKte (e.g., 4 in. above
stack exit or 10 ft after dissipation of water plume).

 "Describe Background - object plume is read against, include
atmospheric conditions (e.g.. hazy).

 "Background Color-blue, white, new leaf green, etc.
 'Required by Reference Method 9; other items
  suggested.
"Required by Method 9 only when particular
  factor could affect the reading.
"Windspced - use Beaufort wind scale or hand-held anomometer;
be accurate to ±5 mph.

"Wind Direction - direction wind is from: use compass: be
accurate to eight points.

"Ambient Temperature - in °F or °C.

""Wet But} Temperature - the wet bulb temperature from the
sling psychrometer.
""Relative Humidity • use sling psychrometer; use local U.S.
Weather Bureau only if nearby.

"Source Layout Sketch - include wind direction, associated
stacks, roads, and other landmarks to fully identify location of
emission point and observer position.

Draw North Arrow - point line of sight in direction of emission
point, place compass beside circle, and draw in arrow parallel
to compass needle.

Sun Location Line • point line of sight in direction of emission
point, place pen upright on sun location line, and mark location
of sun when pen's shadow crosses the observers position.

""Comments - factual implications, deviations, altercations,
and/or problems not addressed elsewhere.

Acknowledgment • signature, title, and date of company official
acknowledging receipt of a copy of VE observation form.

"Obsemstion Date • date observations conducted.
"Start Time, Stop Time - beginning and end times of observation
period (e.g., 1635 or 4:35 p.m.).

"Data Set - percent opacity to nearest 5%; enter from left to right
starting in left column.
"Average Opacity for Highest Period - average of highest 24
consecutive opacity readings.
Number of Readings Above (Frequency Count) - count of total
number of readings above a designated opacity.


"Range of Opacity Readings:
  Minimum - lowest reading
  Maximum - highest reading

"Observer's Name - print in full.
Observer's Signature, Date - sign and date after performing final
calculations.

"Organizttion - observer's employer.

"Certifier. Date - name of "smoke schoor certifying observer and
date of most recent certification.

Verifier. Date - signature of person responsible for verifying
observer's calculations and date of verification.
Figure 4.2.    Reverse side of form. (Continued}

-------
                          Section 3.12.4
April 1983
                                         VISIBLE EMISSION OBSERVA TION FORM
SOURCE NAME
ADDRESS
^^•i^
CITY f r
vn
PHONE '***.
/~
PROCESS EQUIPMENT 1 Ki
vc
S^TE

ZIP
<4OURCE ID NUMBER
r\
u
CONTROL EQUIPMENT ^"~>
DESCRIBE EMISSION POINT
START s~£fPP
HEIGHT ABOVE GROUND IfVfiP
START STOP y^.
DISTANCE FROM OBSERVE&*-
START STOP
OPERATING MODE
OPERA TING MODE



H^GHT RELATIVE TO OBSERVER
'SJART STOP
^DIRECTION FROM OBSERVER
START STOP
DESCRIBE EMISSIONS
START -jLrOP
EMISSION COLOR fn
START STOP ( L
WA TER DROPLETS PRESENT**.
NO O YESO
fiMME TYPE: CONTINUOUS O
FLEITIVEO INTERMITTENT D
4FWA TER DROPLET PLUME:
ATTACHEDO DETACHED D
POINT IN THE PL UME A T WHICH OP A CITY WAS DETERMINED
START STOP
DESCRIBE BACKGROUND
START STOP
BACKGROUND COLOR ^
START STOP /Jf
WIND SPEED 1 l£
START STOP ^-
AMBIENT TEMP.
START STOP
Source Layout Sketch
X
d
Sun-fy Wind^ V?
Plume and = ^Z"T
Stack .-— -\
^^^•^ 14G
SKY CONDITIONS
•S\(RT STOP
'.WfJD DIRECT/ON
'START i
WET BULB TEMP.
Draw North A
(
Emission Point
*ffDserver$ Position
^^--^
Sun Location Line

;rop
RH.percent
rrow
3
COMMENTS /•*— "Sy
f n j
V J
1 HA VE RECEIVED A COPY OfirfWKf OPA CITY OBSERVA TIONS
SIGNATURE fn ff\
T'TLE \nj
DATE
OBSERVATION DATE
^W\
'
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
0






























15






























30 A
(




























START TIME
*^4fr*
II
s"~x



























_^s~»
• «
AVERAGE OPACITY FOR( ,\\
HIGHEST PERIOD \_\j-
/^N
I3'
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
.60
0






























STOP TIME
15






























30






























45






























\UMBER OF READINGS ABOVE
' % WERE
RANGE OF OPACITY READINGS
MINIMUM MAXIMUM
OBSERVER'S NAME (PRINT)
OBSERVER'S SIGNATURE
DATE
ORGANIZATION f f£ J
CERTIFIED BY >*-/
VERIFIED BY
DATE
DATE
                                                                                                                        o
                                                                                                                         o
                                                                                                                           o
Figure 4.3.    Functional sections of visible emission observation form.

-------
                            April! 933
                                                                          Section 3.12.4
  Each major section of the form is
discussed in the following text. A
short explanation of each section's
purpose, a background explanation of
each data element, a description of
the type of information being sought,
and in some cases, appropriate
entries are included. These
discussions are keyed to Figure 4.3 by
corresponding capital letters, and it is
clearly indicated whether information  is
required or recommended.

   A. SOURCE  IDENTIFICATION. Provides
     information that uniquely identifies
     the source and permits the observer
     to locate or make contact with the
     source.
Source name
Address
City
State
Phone
Zip
      Source ID number
Source Name (Required) - include the
source's complete name. If necessary
for complete identification of the
facility, the parent company name,
division, or subsidiary name should be
included.
Address (Required) - Indicate the
street address of the source (not the
mailing  address or the home office
address) so that the exact physical
location of the source is known. If
necessary, the mailing address or
home office address may be listed
elsewhere.
City, State. Zip. Phone
(Recommended) - Self-explanatory.
Source ID Number (Recommended) -
This space is provided for the use of
agency personnel and should be used
to enter the number the agency uses
to identify that particular source, such
as the State file number. Compliance
Data System number, or National
Emission Data System number.

   B. PROCESS AND CONTROL DEVICE
      TYPE. Includes a several word
      descriptor of the process and control
      device, indication of current process
      operating capacity or mode, and
      operational status of control
      equipment.
Process equipment
Control equipment
Operating mode
Operating mode
Process Equipment (Required) - Enter
a description of the process
equipment that emits the plume or
emissions to be read. The description
should be brief but should include as
much information as possible, as
indicated in the following examples:
  Coal-Fired Boiler
  #2 Oil-Fired Boiler
  Wood Waste Conical Incinerator
  Paint Spray Booth
  Primary Crusher
  Fiberglass Curing Oven
  Reverberatory Smelting  Furnace
  Basic Oxygen Furnace
Operating Mode (Recommended) -
Depending on the type of process
equipment, this information may vary
from a quantification of the current
operating rate to  a description of the
portion of a batch-type process  for
which the emission opacity is being
read. For example, entries could
include "90 percent capacity" for a
boiler or "85 percent production rate"
for the shakeout area of a grey  iron
foundry.  For a steel making furnace,
entries would include the exact part of
the process for which readings  are
beipg made, such as "charging" or
"tapping." In some cases, the
observer may have to obtain this
information from  a plant official.
Control Equipment (Required) - Specify
the type(s) of control  equipment being
used in the system after the process
equipment  in question (e.g., "hot-side
electrostatic precipitator").
Operating Mode (Recommended) -
Indicate the degree to which the
control equipment is  being utilized at
the time  of the opacity observations
(e.g., 75% capacity, full capacity, shut
down, off line) and the operating
mode (e.g., automatic). The observer
will probably have to obtain this
information from  a plant official.

   C. EMISSION POINT IDENTIFICATION.
      Contains information uniquely
      identifying the emission point and
      its  spatial relationship with the
      observer's position.
Describe emission point
Start Stop
Height above
ground level
Start Stop
Distance from
observer
Start Stop
Height relative
to observer
Start Stop
Direction from
observer
Start Stop
                                      Describe Emission Point (Required)
                                      Include the identifying physical
characteristics of the point of release
of emissions from the source. The
description must be specific enough
so that the emission outlet can be
distinguished from all others at tf>e
source. In subsequent enforcement
proceedings, the observer must be
certain of the origin of the emissions
that were being read.
  Typical descriptions of the emission
outlet include the color, geometry of
the stack or other outlet, and the
location  in relation to other
recognizable facility landmarks. Any
special identification codes the agency
or source uses to identify a particular
stack or  outlet should be noted along
with the source code used by the
observer. The source of this
information should be recorded (e.g.,
plant layout map or engineering
drawing).
Height Above Ground Level (Required)
- Indicate the height of the stack or
other emission outlet from its
foundation base. This information is
usually available from agency files
engineering drawings, or computer
printouts (such as NEDS printouts).
The information also may be obtained
by using a combination of a
rangefinder and an Abney level or
clineometer. The height may also be
estimated.
Height Relative to Observer (Required)
- Indicate an estimate of the height of
the  stack outlet (or of any other type
of emission outlet) above the position
of the observer.  This measurement
indicates the observer's position in
relation  to the stack base (i.e., higher
or lower than the base) and may later
be used in slant angle calculations
(see Section 3.12.6 and Subsection
4.4.6) if such calculations become
necessary.
Distance From Observer (Required) -
Record the distance from the point of
observation to the emission outlet.
This measurement may be made by
'using a  rangefinder. If necessary, a
map also may be used to estimate the
distance.
   It  is important that this
measurement be reasonably accurate
if the observer is close to the stack
(within 3 stack heights) because it is
coupled with the outlet  height relative
to the o')server  to determine the slant
angle at which the observations were
made (see Figure 4.4). A precise
determination of the slant angle may
become important in calculating any
positive  bias inherent in the opacity
readings.
Direction From Observer (Required) -
Specify the direction of the  emission
point from the observer to the closest
                                                                                          K
                                                                                             n\

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                        Section 3.12.4
                                                      10
                                    April 1983
of the eight points of the compass
(e.g., S, SE, NW, NE) or 45°. Use of a
compass to make this determination
in the following manner is suggested:
hold the compass while facing the
emission point;  rotate the compass
until the North compass point lies
directly beneath the needle (which
will be pointing towards magnetic
North); then the point of the compass
closest to the emission outlet will
indicate the direction (Figure 4.5). A
map (plant layout) also may be used to
make this determination.
Describe Emissions (Required) -
Include both the physical'
characteristics of the emissions not
recorded elsewhere on the form and
the behavior of the resultant plume.
The description of the physical
characteristics might include terms
such as lacy,  fluffy, and detached
nonwater vapor condensibles.
  The terminology  illustrated in Figure
4.6 can be used to describe  plume
                  Stack
Observer/   Slant
     ,'V5° Angle
behavior. The behavior can be used to
determine the atmospheric stability on
the day of the opacity observations.
Emission Color (Required) - Note the
color of the emissions. The plume
color can sometimes be useful in
determining the composition of the
emissions and will also serve to
document the total contrast between
the plume and its background as seen
by the opacity observer during the
observation period.
Plume  Type (Recommended) - Check
"continuous" if the duration of the
emissions being observed is greater
than 6  minutes. Check "intermittent"
if the opacity cycle is less than 6
minutes. Check "fugitive" if the
emissions have no specifically
designated outlet.
Water Droplets Present (May be
required) - Check "yes" or "no" as
appropriate. In some cases, the
presence of condensed water vapor in
the plume can be easily observed.
                                                    L' - Observer Path Length
                                                    L - Actual Path Length
                              Height
                              Relative to
                              Observer
     Distance from observer

Figure 4.4.   Slant angle relationships.
Observer
   c™
                                                                    Stack
                             -o
                                 Compass

Figure 4.5.    Direction from observer is NE.
   D. EMISSIONS DESCRIPTION. Includes
     information that definitely
     establishes what was observed
     while making the visible emissions
     determination.
Describe emissions
Start Stop
Emission color
Start Stop
Plume type: Continuous D
Fugitive O Intermittent D
Water droplets
present
NoO YesD
tf water droplet plume
Att ached Q
Detached D
Point in the plume at which opacity was
determined
Start Stop
Plumes containing condensed water
vapor (or "steam plumes") are usually
very white, billowy, and wispy at the
point of dissipation, where the opacity
decreases rapidly from  a high value
(usually 100%) to 0 percent if there is
no residual opacity plume contributed
by contaminate'in the effluent.
  To document the presence or
absence of condensed water vapor in
the plume, the observer must address
two points. First, is sufficient  moisture
present (condensed or uncondensed)
in the plume initially? Second, if
enough moisture is present, are the
in-stack and ambient conditions such
that it will condense either before
exiting the stack or after exiting (wtien
it meets with the ambient air)? The
first question can be  answered  by
examining the process  type and/or
the treatment of the effluent gas after
the process. Some common sources
of moisture in the plume are:
  O  Water produced  by combustion
     of fuels,
  O  Water from dryers.
  O  Water introduced by wet
     scrubbers,
  O  Water introduced for gas cooling
     prior to an electrostatic
     precipitator, or other control
     device, and
  O  Water used to control the
     temperature of chemical
     reactions.
  If water is present in the plume.
data from a sling psychrometer, which
measures relative humidity, in
combination with the moisture
content and temperature of the
effluent gas can be used to predict
whether the formation  of a steam
plume is a possibility (see Section
3.12.6).
// Water Droplet Plume: (May  be
required) - Check "attached"  if
condensation of the moisture
contained in the plume occurs within
the stack and the steam plume  is
visible at the stack exit. Check
"detached" if condensation occurs
some distance downwind from the
stack exit and the steam plume and
the stack appear to be unconnected.
Point in the Plume at Which Opacity
was Determined (May be required) *
Describe as succinctly as possible the
physical location in the plume where
the observations were made.  This
description is especially important hi
the case where condensed water
vapor and/or secondary plume  is
present. For example, were the
readings made prior to formation of
the steam plume? If the readings were
made subsequent to dissipation (e.g.,
in the case of an attached steam
o
                                                                           o
                                                                                                                 o

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                             April 1983
                                                        11
           Section 3.12.4
              Coning
              Fanning
                                                                                              Lofting
                                                      Looping
                                                                                             Fumigation
Figure 4.6.    Plume behavior descriptors.
plume), then specify how far
downwind of the dissipation point and
how far downwind of the stack exit
the reading was made. This
information can be used to estimate
the amount of dilution that occurred
prior to the point of opacity  readings.
Descriptions such as 4 feet  above
outlet and 80 feet downstream from
outlet, 10 feet after steam dissipation
are appropriate.
  Figure 4.7 shows some examples of
the correct location for making opacity
readings in various steam plume and
'secondary plume situations.
Describe Background (Required) -
Describe the background that the
plume is obscuring and against which
the opacity is being read. While
describing the background,  note any
imperfections or conditions, such as
texture, that might affect the, ease of
making readings. Examples  of
background descriptions are roof of
roof monitor, stand of pine trees, edge
of jagged stony  hillside, clear blue sky,
stack scaffolding, and building
obscured by haze.
Background Color (Required) -
Accurately note the  background color
(e.g., new leaf green, conifer green,
brick red, sky blue, and gray stone).
  £. OBSERVA TION CONDITIONS.
     Covers the background and ambient
     weather conditions that occur during
     the observation period and could
     affect observed opacity.
Describe background
Stan Stop
Background color
Start Stop
Windspeed
Start Stop
Sky conditions
Start Stop
Wind direction
Start Stop
Ambient temp. Wet bulb
Start Stop temP
Relative humidity
                                                                           Area of Steam
                                                                           Condensation
                                       Attached steam plume.
                                                                                           'Read Here
                                                                                   Area of Steam
                                                                                   Condensation  I
                                       Detached steam plume. In
                                       rare cases, it may be
                                       necessary to make readings
                                       at the point of steam dis-
                                       sipation if the plume is
                                       more opaque at that point.
Read Here <
(preferred)
                                  Or Here
                                 Point of Steam
                                 Dissipation
          I  Area of Steam
          I  Condensation
                                                                                             Secondary Plume Formation}
                                                                                                     (Acid Mist)       I
                            Point of Steam
                            Dissipation
                                       Plume from a sulfuric acid
                                       plant with detached steam
                                       plume. Plume is clear at
                                       stack exit. Secondary acid
                                       mist is formed in area of
                                       steam condensation.
                                       Figure 4.7.    Location for reading opacity under various conditions.

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                         Section 3.12.4
                                                       12
                                    April 1983
Sky Conditions (Required) - Indicate
the percent cloud cover of the sky.
This information can be indicated by
using straight percentages (e.g., 10%
overcast, 100% overcast) or by
description, as shown below.
Term
Clear
Scattered
Broken
Overcast
Amount of cloud cover
<10%
10% to 50%
50% to 90%
>90%
Windspeed (Required) - Give the
windspeed accurately to ±5 miles per
hour. The windspeed can be
determined using a hand-held
anemometer (if available), or it can be
estimated by using the Beaufort Scale
of Windspeed Equivalents in Table
4.1.
Wind Direction (Required) - Indicate
the direction from which the wind is
blowing. The direction should be
estimated to eight points of the
compass  by observing which way the
plume is  blowing. If this type of
estimation is not possible, the
direction  may be determined by
observing a blowing flag or by noting
the direction a few blades of grass or
handfull of dust are blown when
tossed into the air. Keep in mind that
the wind direction at the observation
point may be different from that at the
emission point; the wind direction at
the emission point is the one of
interest.
Ambient Temperature  (Required) - The
outdoor temperature at the plant site
is measured by a thermometer (in
degrees Fahrenheit  or centigrade)
obtained from a local weather bureau
or estimated. Be certain to note which
temperature scale is used. This is
done in conjunction with the wet
bulb temperature and  is only needed
when there are indications of a
condensing water droplet plume.
Wet Bulb Temperature (May be
required) - Record the wet bulb
temperature from the  sling
psychrometer. This  is to be done only
when there are indications of a
condensing water droplet plume.
Relative Humidity (May be required) -
Enter the relative humidity measured
by using a sling psychrometer in
conjunction with a psychrometric
chart. This information can be used to
determine if water vapor in the plume
will condense to form a steam plume
(see Section 3.12.6). If a sling
psychrbmeter is not available, data
from a nearby U.S. Weather Bureau
can be substituted.
Table 4.1.    The Beaufort Scale of Windspeed, Equivalents
General
description
Calm


Light

Gentle

Moderate

Fresh





Strong




Gale



Whole gale

Hurricane
Specifications
Smoke rises vertically
Direction of wind shown by smoke
drift but not by wind vanes
Wind felt on face: leaves rustle;
ordinary vane moved by wind
Leaves and small twigs in constant
motion; wind extends light flag
Raises dust and loose paper; small
branches are moved
Small trees in leaf begin to sway;
crested wavelets form on inland
waters
Large branches in motion; whistling
heard in telegraph wires; umbrellas
used with difficulty
Whole trees in motion; inconven-
ience felt in walking against the
wind
Twigs broken off trees; progress
generally impeded
Slight structural damage occurs
(chimney pots and slate removed)
Trees uprooted; considerable
structural damage occurs
Rarely experienced; accompanied
by widespread damage

Limits of velocity
33 ft (JO m) above
level ground, mph
Under 1

1 to 3

4 to 7

8 to 12

13 to 18


19 to 24


25 to 31


32 to 38

39 to 46

47 to 54

55 to 63

64 to 75
Above 75
    F. OBSERVER POSmON AND SOURCE
      LAYOUT. Clearly identifies the
      observer's position in relation to the
      emission point, plant landmarks.
      topographic features, sun position.
      and wind direction.
                   o
                                                                             Source Layout Sketch     Draw North Arrow
                                                                                                         O
 Sun-fy Wi
    Plume and —
    Stack
                                                                                            X Emission Point
Observers Position
                140°

           Sun Location Line
Source Layout Sketch (Required) -
This sketch should indude as many
landmarks as possible. At the very
least, the sketch should locate the
relative position of the observed outlet
in such a way that it will not be
confused with others at a later date,
and clearly locate the position of the
observer while making the VE
readings. The exact landmarks will
depend on the specific source, but
they might include:
   O Other stacks
   O Hills
   O Roads
   O Fences
   O Buildings
   O Stockpiles
   O Rail heads
   O Tree lines
   O Background for readings
   To assist in subsequent analysis of
the reading conditions, sketch in the
plume (indicate the direction of wind
travel). The wind direction also must
be indicated in the previous section.
Draw North Arrow (Recommended) -
To determine the direction of north.
point the line of sight in the source
layout sketch in the direction of the
actual emission point, place the
compass next to the circle and draw
an arrow in the circle parallel to the
compass needle. A map (plant layout)
may also be used to determine
direction north.
Sun's Location (Recommended) - It is
important to verify this parameter •
before making any opacity readings.
The sun's location should be within
the 140° sector indicated in the layout
sketch; this confirms that the sun is
within the 140° sector to the
observer's back.
   To draw the sun's location, point the
line cf sight in the source layout
sketch in the direction of the actual
emission point, place a pen upright
along the "sun location line" until the
                   O
                                                                                                                 o

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                            April 1983
                 13
                                     Section 3.12.4
shadow of the pen falls across the
observer's position. Then draw the
sun at the point where the pen
touches the "sun location line."

   G.  COMMENTS. Includes all
      implications, deviations,
      disagreement with plant personnel
      and/or problems of a factual nature
      that have bearing on the opacity
      observations and that cannot be or
      have not been addressed elsewhere
      on the form.
 Comments
Comments (May be required) - Note
all implications, deviations,
disagreements with plant personnel,
or problems of a factual nature that
cannot be or have not been addressed
elsewhere on the form. Examples of
points to be included in this section
are:
  G  Changes in ambient  conditions
     from the  time  of  the  start  of
     readings.
  O  Changes in plume color,
     behavior, or other characteristics.
  O  Changes in observer position and
     reasons for the change; a new
     form should also be  initiated in
     this case so that a new source
     layout sketch  may be drawn.
  O  Difficulties encountered in plant
     entry.
  O  Conditions that might interfere
     with readings or cause them to
     be biased.
  O  Drawing of unusual  stack
     configuration  (to show multiple
     stacks or stack in relation to roof
     line).
  O  Suspected changes to the
     emissions or process during
     observation.
  O  Unusual process conditions.
  O  Additional source identification
     information.
  O  Type of plant (if not specified
     elsewhere).
  O  Reasons for missed readings.
  O  Other observers present.

   H. COMPANY ACKNOWLEDGEMENT.
     Company acknowledgement of. but
     not necessarily agreement with, the
     opacity observations stated on the
     form.
1 have received a copy of these opacity
observations
Signature
Title
Date
Signature (Recommended) - This
space is provided for the signature of
a plant official who acknowledges that
he/she has received a copy of the
observer's opacity readings. His/her
signature does not in any way
indicate that he/she or the company
concurs with those readings.
Title (Recommended) - Include the
acknowledging official's company title.
Date (Recommended) - The company
official should enter the date of
acknowledgment.

    /. DA TA SET.  Opacity readings for the
      observation period, organized by
      minute and second. This section
      also includes the actual date and
      start and stop times for the
      observation period.
Observation
date
fr^S.
1
2

29
30
0





15





30





Start time
45





M-^
31
32

59
60
0





Stop time
15





30





45





Observation Date (Required) - Enter
the date on which the opacity
observations were made.
Start Time. Stop Time (Required) -
Indicate the times at the beginning
and the end of the actual observation
period. The times may be expressed in
12-hour or 24-hour time (i.e., 8:35
a.m. or 0835); however, 24-hour time
tends to be less confusing.
Data Set (Required) - Spaces are
provided for entering an opacity
reading every 15s for up to a 1-hour
observation period. The  readings
should be in percent opacity and
made to the nearest 5 percent. The
readings are entered from left to right
for each numbered minute, beginning
at the upper left corner of the left-
hand column, labeled row "M 1"
(minute 1) and column "s  0" (0
seconds). The next readings are
entered consecutively in the spaces
labeled  M 1, s 15; M 1,  s 30; M 1, s
45; M 2, sO, M 2, s 15, etc.
   If, for any reason, a reading is not
made for a particular 15-second
period, that space should be skipped
and an explanation  should be provided
in the comments section. Also a dash
(-) should be placed in the space
which denotes that  the space is not
just an oversight.
   J. DATA REDUCTION. Basic analysis of
     the opacity readings to  allow
     preliminary compliance appraisal in
     accordance with EPA Reference
     Methods.
Average opacity
for highest period
Number of read-
ings above
% were
Range of opacity readings
Minimum Maximum
Average Opacity for the Highest
Period (Required) - Enter the average
of the sum of the highest 24
consecutive readings (6-minute set).
In other words, identify the 24
consecutive readings that would sum
to the greatest value and then divide
this value by 24 to get the average
opacity for that set of readings. Note:
The average should not include a time
lapse for which a valid reading could
have been taken but was not (see    -
Section 3.12.6).
Number of Readings Above... % Were ,
... (Recommended) - Indicate an       ,
optional frequency count of the
opacity readings above a particular
value. The value is chosen according
to the opacity standard for the
emission point and is generally the
actual value of the standard.
   Method 9 does not specify the use
of frequency counting to reduce data,
but many  States use it to determine
compliance with their time exemption
opacity standards. For example, a
State regulation might specify that
opacity of a specific type of emission
source is not to exceed 20 percent for.
more than 3 minutes  in an hour. If
more than 12 readings out of 240
exceed 20 percent in an hour-long
observation period, that State may
consider that source out of
compliance. For example,
   14  readings out of 240 readings (1
   hour) are above 20 percent opacity
   14  x 15 s per  reading = 210s
   = 3.5 minutes of readings above the
   standard.
Range of Opacity Readings (Required)
- Enter the highest and lowest opacity
readings taken during the specified
observation period.

    K. OBSERVER DATA. Information
      required to validate the opacity data.
Observer's name (print)
Observer's signature
Date
                                                                            Organization
                                                                            Cert if fed by
                     Date
                                                                            Verified by
                     Date

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                        Section 3.12.4
                 14
                                    April 1983
Observer's Name (Required) - Print
observer's entire name.
Observer's Signature/Date
(Recommended) - Self-explanatory.
Organization (Required) - Provide the
name of the agency or company that
employs the observer.
Certified By (Recommended) - Identify
the agency, company, or other
organization that conducted the
"smoke school" or VE training  and
certification course where the
observer obtained his/her most
current certification.
Date (Required) - Provide the date of
the most current certification.
Verified By (Recommended) - The
actual signature of someone who has
verified the opacity readings and
calculations, usually  the observer's
supervisor, or the individual who is
responsible for his/her work.
Date (Recommended) - Provide the
date of verification.

4.3.3  Facility Operating Data  - It is
strongly recommended that  a VE
inspection/observation conclude with
a source inspection if opacity values
are in excess of the standard. The
observer would  first follow the  plant
entry procedure in Subsection 4.1  and
then follow the  indicated procedure to
obtain facility operating data.

  After the VE determination, it is
recommended that the following
source information be determined:
  1. Were the plant and the source of
     interest operating normally at the
     time  of the VE evaluation?
  2. Are there any control devices
     associated with  the source?
  3. Were the control devices
     operating properly?
  4. Have there been any recent
     changes in the operation of the
     process or control devices?
  5. Have any malfunctions or
     frequent upsets in the  process or
     control devices been noted and
     reported (if required by the
     agency)?
  6. Is the plant operator aware of
     excessive visible emissions and
     have any corrective steps  been
     taken to alleviate the problems?
  7. Are there any other sources of
     visible emissions in close
     proximity to the source in
     question that may interfere with
     reading the plume opacity or
     contribute  to the appearance of
     the plume?

4.3.4 Photographs  - It is suggested
that photographs be taken before and
after the observation is made, not
during the observation period.
Conditions should be recorded as ney
existed at the time of the observation
The use of a 35-mm camera is
recommended to ensure good
photogra'phs.
  Each photograph should be identified
with the date and time, the source.
and the position from which the
photograph was taken.

4.4  Special Observation Problems
  The VE observer constantly should
be aware that  his/her observations
may be used as the basis of a
violation action and subject to
questioning as to the reliability of the
observations. Therefore, he/she must
also be aware that under some
conditions or situations it may be
difficult or impossible to conduct a
technically defensible visible
emissions observation.
  This section discusses  some of the
most prevalent difficult conditions or
special problems associated with the
visible emission observation. Each
discussion is directed toward defining
the problem, indicating how it might
invalidate readings taken, and
addressing possible solutions and/or
ways to minimize the invalidating
effects.
  Not all of these discussions offer a
complete  solution for a particular
problem; thus, it is important for the
individual observer to keep in mind
the purpose of the visible emission
observation when  considering exactry
what action to take when faced with a
special problem.

4.4.1  Positional Requirements -
Valid VE evaluations can be
conducted only when the sun is
properly positioned at the observer's
back. Failure to adhere to this
positioning can result in significant
positive bias caused by forward light
scatter in opacity readings. Because of
this overriding constraint, some times
and  locations  make it difficult for the
observer to meet other opacity reading
criteria, e.g., reading the narrow axis
of a  rectangular stack, reading a
series of stacks across a  short axis to
prevent multiple plume effects,  and
obtaining  a contrasting background.
Plant topography also may generate
constraints that restrict viewing
positions to  one or more  locations.
The observer will be aided in
determining the best observation
location by following the criteria listed
below.

  1.  Make sure that the emission
     point is north of the observation
     point.
  2.  Obtain a clear view of the
     emission point with no
     interfering plumes.
  3.  Be sure that rectangular stacks
     are read across the narrow axis
     and multiple stacks are read
     perpendicular to the line of
     stacks.
  4.  Minimize the slant angle by
     moving a sufficient distance from
     the stack or to an elevated
     position (see Subsection 4.4.4).
  5.  Find a contrasting background or
     a clear sky background.
  6.  Finally, determir>e the best time
     of day for observations  based on
     the daily sun tracks at that
     location.

  Collaborative studies of  the
performances of trained observers
have indicated that, with the
exception of the positive bias caused
by having the improper sun angle,
visible emission observation biases
tend to be negative. Thus, if viewing
conditions are not  ideal and a
negative bias (lower value) results,
opacity readings may  not provide the
true measure of plume opacity
required to correlate to mass
emissions or control equipment
efficiency. However, readings that
indicate a violation can be regarded as
the minimum opacity; therefore,
documentation of the violation is
valid.
  In situations where the  observer
must make plume  opacity readings
when all the criteria for correct
viewing cannot be met. all
extenuating circumstances must be
documented on the VE evaluation
form.

4.4.2  Multiple Sources/Multiple
Stacks - An observer  is sometimes
compelled to evaluate a stack that
discharges emissions from more than
one source or to evaluate a  single
source that has more than one
emission point.
  In the case where one stack serves
more than one emission source, the
observer may be able to isolate the
emissions from one source as a result
of intervals of operation, or by
requesting the facility's cooperation in
temporarily shutting down the other
source(s). Otherwise,  the  observer
should proceed with the VE
observation and document the
situation completely on the VE
evaluation form.
  In the case of multiple emission
points for a single  source  (e.g., in
positive-pressure baghouses and
multiple vents in roof  monitors).
Section 2.1 of Method 9 directs the
o
o
 o

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                             April 1983
                                                       15
                                     Section 3.12.4
 observer to read multiple stacks
 independently if it is possible to do so
 while meeting sun position
 requirements. If it is necessary to get
 an overall  reading for the group of
 stacks, the following set of formulas
 can be used to calculate this reading
 from the individual opacity values.
                   100
                   100

           i x T2 x .... TN = TT

           100 x(1 -TT) = OT
 where
 Oi= % opacity of 1st plume
 02= % opacity of 2nd plume '
 ON= % opacity of nth plume
 Ti = Transmittance of 1st plume
 T2= Transmittance of 2nd plume
 TN= Transmittance of nth plume
 TT= Total transmittance
 OT= % total opacity
4.4.3  High Winds - Occasionally the
crosswind conditions are unfavorable
during field observations of plume
opacity. When the winds are strong
enough to shear the emissions at the
stack outlet, it is difficult for the
observer to  make an accurate and fair
VE observation. Strong crosswinds
can have several effects on the
plume:
  1.  The plume becomes essentially
     flattened and is no longer conical
     in shape thus the path length
     and apparent opacity increases.
  2.  The plume is torn into fragments
     and becomes difficult to obtain a
     representative  reading.
  3.  The plume becomes diluted, and
     the  apparent opacity is lowered.

  The observer can compensate
somewhat for the effect of flattening
by reading the plume downwind of
the stack, after it has reformed into a
cone. The dilution effect of high
winds, which lowers the apparent
opacity, presents more of a problem.
Because  of the negative bias
introduced, the effectiveness of
Method 9 as a control tool under
these conditions is diminished. If a
violation  is still observed under these
conditions, it should be considered
valid. It is recommended that
• »b*A*«Ai,Af faactima \/P ohciaruatinn?; bfi
 suspended until the wind-caused
 interferences have abated.

 4.4.4  Poor Lighting - Poor lighting
 conditions for VE observations usually
 involve one or more of the following:
 (1) a totally overcast sky, (2) early
 morning or late afternoon hours, or (3)
 nighttime. Each of these three lighting
 conditions has the same net effect on
 the plume;jhey-differ slightly only in
 the cause of the poor illumination.
 When the amount of available
 sunlight is below a certain level, the
 contrast between a white plume and
 the background decreases. Therefore,
 readings are not recommended in
 either the early morning hours (at or
 approaching dawn) or late afternoon
 hours (at or approaching dusk).
    Nighttime viewing obviously
 represents the most severe of poor
 lighting conditions. Some agencies
 have attempted, with mixed results, to
 use night vision devices (light
 intensification scopes) for plume
 viewing and testing in the dark.
 Others have achieved better results by
 placing a light behind the emissions,
 which provides a  very high contrast
 background. For this method, it is
 important to select a source of light of
 moderate strength that does not
 cause the iris of the eye to close.

 4.4.5  Poor Background - The color
 contrast between  the plume and the
 background against which it is viewed
 can affect the  appearance of the
 plume as viewed by an observer. Field
 studies have corroborated predictions
 of the plume opacity theory by
 demonstrating that a plume is most
 visible and has the greatest apparent
 opacity when viewed against a
 contrasting background.

   Consistent with these findings is
 the fact that with  a high contrast
 background, the potential for positive
 observer bias is the greatest.
 However,  field trials consisting of 769
 sets of 25 opacity readings each have
 shown that for more than 99 percent
 of the sets/the positive observer error
 was no greater than 7.5 percent
"opacity.2
   Also consistent  with these findings
 is the fact that as  the contrast
 between the plume and its
 background decreases, the apparent
 opacity decreases; this greatly
 increases the chance for a negative
 observer bias. Under these conditions,
 the likelihood lessens of a facility
 being cited for a violation of an
 opacity standard because of observer
 error.
  When faced with a situation where
there is a choice of backgrounds, the
observer should always choose tie
one providing the highest contrsst
with the plume because it will permit
the most accurate opacity reading.
However, if a situation arises where
other constraints  make it impossible
to locate an observation point that
provides a high contrast background,
the observer may read against a less
contrasting one with.confidence that a
documented violation shouldbe
legally defensible.                  ;

4.4.6 Reduced Visibility -
Environmental factors at the time of
observation also are of concern 10
the visible emissions observer.
Environmental considerations indude
rain, snow, or other forms of
precipitation, and photochemical smog
buildup, fog, sea spray, high humidity
levels, or any other cause of haze.
These environmental factors create a
visual obscuration that can increase
the apparent opacity of the plums, but
more commonly reduce the
background contrast and thus
decrease the apparent opacity.
  In recognition of the problems that
could result from  reduced visibiftty
caused by environmental factors, the
amended Method 9 (November 12,
1974) states, in paragraph  2.1 of the
Procedures Section: "The qualified
observer shall stand at a distance
sufficient to provide a clear view of
the emissions ..." A "clear view"
must be interpreted as a view free
from obstacles or interferences. Most
problems caused  by reduced visibility
can be alleviated  simply by making
the observations on another day.

4.4.7  Tall Stacks/Slant Angle -
When an observer's distance from the
stack approaches  1/4 mile
(approximately 1300 feet, or a Irate
over four football fields), the ambient
light scattering may begin to have an
adverse effect on the contrast
between the plume and the
background. Also, if the sky is
overcast or hazy on the day of
observation, the farther the observer
is from the emission point,  the more
the haze interferes with the view of
the plume and hence, the less rentable
the readings.
  On the other hand, the
recommendation that the' observer
stand at least three stack heights from
the stack being observed is intended
to ensure that the width of the plume
as it is viewed is approximately the
same as it is at the stack outlet. As
the observer gets closer to the stack
and the viewing (slant) angle

-------
                        Section 3.12.4
                                                      16
                   I
                                                                         April 1983
                                      o
increases, the observed path length
also increases; this causes the
observed opacity to increase because
the observer is reading through more
emissions. These relationships are
shown in Figure 4.8. At an observer
distance of three stack heights, which
corresponds  to a slant angle of  18°,
the deviation of observed opacity from
actual opacity decreases to 1 percent
opacity, which is considered
acceptable (see Section 3.12.6).
  The three-stack-heights relationship
only occurs if the 6bserver\and the
base of the stack are in the\same
horizontal plane. If the observer is on
a higher plane than the base of the
stack, then the minimum distance for
proper viewing can be reduced to less
than three stack heights; conversely,
if the observer's plane is lower than
that of the stack base, then the
minimum suggested distance will be
greater than  three stack heights (see
Figure 4.8). The real determining
factor is the  slant angle. To assure no
more than a  1  percent opacity
deviation of observed opacity from
actual opacity, the observer must heve
a visual slant angle of 18° or less.

4.4.8  Steam Plumes - Under certain
conditions, water vapor present in ar
effluent gas stream will condense to
form a visible water droplet or "stear"
plume. Because the NSPS (specifically
Method 9) and almost all SIP's
exclude condensed, uncombined
water vapor from opacity regulations.
the VE observer must be careful that
he/she does not knowingly read a
plume at a point where condensed
water vapor,is present and record the
value as representative of stack
emissions.
  Knowledge of the kind of process
that generates the emissions being
read and simple observation of the
resultant plume almost always allows
the observer to determine if a steam
plume  is present. Steam plumes are
commonly associated with processes
or control equipment that introduce
water vapor  into the gas stream.
These sources include:             ;
   O Fuel combustion,
   O Drying operations,
                                                   Plume
                                                               H
                                    •5H
Figure 4.G.    Observer distance, observed path length relationships.
  O Wet scrubbers,
  O Water-induced gas cooling prior
    to an emissions control device,
    and
  O Water-induced chemical reaction
    cooling.
  Also, observation of steam plumes
will reveal that they are usually very
white, billowy, and have an abrupt
point of dissipation. At the point of
dissipation, the opacity generally
decreases rapidly from a high value
(usually 100%) to a low value.
Depending on the moisture and
temperature conditions  in the stack
and in the ambient air, steam plumes
may be either "attached" or
"detached." An attached steam plume
forms within  ^he stack and is visible
at the exit; a  detached steam plume
forms downwind of the stack exit and
does not appear to be connected to
the stack. In cases when it is not clear
whether a steam plume is present or
when an observer would like to
predict the formation of a steam
plume, the stack gas conditions may
be used in conjunction with the
ambient relative humidity to make the
prediction (see Section 3.12.6).
  When a steam plume is present, the
paniculate plume is read at a point
where 1) no condensed water vapor
exists, and 2) the opacity is the
greatest. In the case of a detached
steam plume, this point is usually at
the stack exit, prior to the water vapor
condensation; in the case of an
attached steam plume, it is usually
slightly downwind of the point of
steam plume dissipation (for
examples, see Figure 4.7). The observer
should always carefully document the
point chosen.

4.4.9  Secondary Plume Formation -
Some effluent gas streams contain^
species that form visible mists or
plumes by a physical and/or chemical
reaction that  occurs either at some
point in the stack or after the
emissions come in contact with the
atmosphere. This situation is known
as secondary plume formation.
Examples of such secondary plume
formation include:

   O A change in the physical state, of
     a compound condensing from a
     gas into a liquid, such as
     vaporized hydrocarbon .
     condensing into an aerosol or a
     solid.
   O A physiocochemical reaction
     between two or more gaseous (or
     in some cases, liquidj.species in
     a plume, such as the, .
   ;• condensation of ammonia, sulfur
   1  dioxide, and water vapor to form
                                                                                                                 O
                                                                                                                 o

-------
                            April 1983
                                                       17
                                                                          Section 3.12.4
     paniculate ammonium sulfite or
     the condensation of sulfur
     trioxide and water vapor to form
     sulfuric acid mist.
   O A physiocochemical reaction
     between species in a plume and
     species in the atmosphere, such
     as the formation of N203.
   Secondary plumes are sometimes
 found in the  following processes (with
 these suspected secondary reactions):
   O Coal- and  oil-fired cement kilns
     (SO3 + H2O - H2S04 mist)
     or [NH3 + S02 + H2O -
     (NH«)2 S03]
   O Fossil-fuel-fired steam
     generators (S02 + H2O — H2SO<
     mist)
   O Sulfuric acid manufacturing (SO3
     + H2O — H2SO4 mist)
   O Plywood and particleboard wood
     heating (organic vapor — organic
     mist)
   O Glass manufacturing (inorganic
     vapor — organic aerosol).
  As in the case of steam plumes,
 secondary plumes can be attached or
 detached, depending on the specific
 condensation reaction and the
 ambient conditions. For example, a
 secondary plume will be attached if a
 reaction between plume species
 occurs in the stack and the stack
 temperature is sufficiently low to
 cause condensation of the reaction
 products to a visible liquid or solid
 phase. A detached secondary plume
 will be evident when the reaction
 does not occur until the gas stream
 comes in contact with the
 atmosphere. The degree of
 detachment depends on the ambient
 conditions, the degree of mixing
 between the effluent and the
 atmosphere, and the specific
 reaction(s) involved.
  Secondary plumes may occur with
 or without an accompanying steam
 plume, and it is important that the
 observer be able to distinguish
 between the two. Unlike steam
 plumes, secondary plumes are often
 persistent (they do not dissipate
 rapidly), are usually bluish white (due
 to the fine particles present), and are
 grainy rather than billowy.
  To read  a secondary plume, the
 observer must locate the densest
 point of the plume where water vapor
 is not evident and make the readings
 at that point. This point may occur in
 several different areas, depending on
the type of secondary plume. An
 attached secondary plume will usually
 be read at the stack exit if an  attached
steam plume is  not present; if an
 attached steam  plume is present, the
 secondary plume must be read at the
point of steam dissipation. A ceTached
secondary plume will usually -~ read
slightly downwind of the ares ;•"
formation, assuming there is r;
interfering condensed water vaoor.
Under some conditions, a seciy-dary
plume may not fully condense ..ntil
some distance downstream o-> :~e
point of formation; in this case the
observer simply looks for the Densest
area of the plume and makes tie
reading at that point. It is especially
important in reading a seconc=~y
formation plume to describe fully the
point at which the reading was taken
and the exact appearance of \-~
plume. (Refer to  Figure 4.7 for one
example of where to read a secondary
plume.)

4.4.10  Fugitive Emissions - Fugitive
emissions are those emissions that do
not emanate from a conventional
smoke stack or vent. Examples of
these nonconventional emissions
include:
  O Dusty or unpaved roads
  O Stock or raw material piles under
     windy conditions or when moved
     by machinery
  O Conveyor belts, pneumatic lifts,
     clamshells,  and draglines
  O Cutting, crushing, grinding, and
     sizing  of minerals or othe'
     materials
  O Plowing, tilling, and bulldozing
  © Open incineration
  O Demolition activities
  O Roof monitors or building vents,
     especially in foundries, iron and
     steel facilities, and related
     industries.
  Because of the irregular shape of
their emission point or area,
conducting a conventional Method 9
test on fugitive emissions may appear
difficult; however, it usually involves
only relatively minor adjustments.
Commonly  used procedures for
observation of fugitive emissions are
listed below:
  1.  If possible, isolate the particular
     emission from other emissions
     by choosing an appropriaie
     position for  observation.
  2.  Adhere to the lighting
     requirements of Method 9 by
     keeping the sun in the 14O"
     sector to the observer's beck.
  3.  Also adhere to Method 9 in
     selecting a position with regard
     to wind direction and a
     contrasting  background.
  4.  Whenever possible, select the
     shortest path length through the
     plume.
  5.  Before taking readings, view the
     emission for several minutes to
     determine its characteristics.
     Changes that may occur in the
     airborne paniculate pattern ove'
     time are important to note and :c
     consider in selecting a viewing
     point.
   6. Select the line of sight and the
     viewing point in the emissions sc
     that,-on the average, the denses:
     part of the emissions will be
     observed. It is recommended tha:
     all subsequent readings in a date
     set be taken at the same relative
     position to the emission source.
   7. The configuration of the emission
     point or area may necessitate
     taking readings at a point
     downwind where the emissions
     have assumed a more
     conventional plume shape.
   8. If the plume cannot be viewed
     through a nearly perpendicular
     angle, corrections may be
     necessary.


4.4.11   Intermittent Sources - Some
sources release visible emissions
intermittently rather than
continuously; e.g., coke ovens, batch
operations, single chamber
incinerators, malfunctioning control
equipment (in rapping, bag shaking,
etc.), boilers during soot blowing, and
process equipment during startup.
  Intermittent emissions may have a
high opacity for a short time and a
low or negligible opacity at other
times. This high-low cycle may be
repeated at fairly regular intervals. If s
source is in violation (or in continuous
compliance) of the applicable standard
over the 6-minute averaging time
required by Method 9, it does not
pose a problem to the visible
emissions observer. If the pollutant-
emitting operational cycle of a source
is  less than 6 minutes in duration,
however, that source may be out of
compliance only for a portion of each
6-minute averaging period, which will
make it  difficult or  impossible to
document a violation if the data is to
be reduced to a 6-minute average.
  If the  source is not covered by a
NSPS or a State  Implementation Plan
that specifies the explicit use of
Method 9 or another specified
modification to Method 9, another
technique for reading intermittent
emissions of less than a 6-minute
duration is to use Method 9
procedures but reduce the averaging
time to about 3 minutes. This
reduction will allow the observer to
tally the number of 3-minute
violations that occur. Analysis of
many data sets has confirmed that
using this method sacrifices little or
no accuracy.

-------
Section 3.12.4
                              18
April 1983
In all cases where sources are not Table4.2. Activity Matrix for Visible Emission Determination
subject to NSPS or other federally Frequency and Action if
promulgated standard, the existing Acceptance method of requirements
State regulations and specified opacity ^^ ,imits measurement are not me:
observation methods (if any) must be
used. Two other techniques that have Perimeter survey
been used to document intermittent
emissions are the "stopwatch"
technique (measuring the total
accumulated time that the opacity
exceeds the applicable standard) and Plant entry
the time-aggregate data reporting
technique (taking readings every 15
seconds, tallying the number of
readings exceeding the standard, and
multiplying this number by 1 5 seconds
to determine the amount of time the
source is out of compliance during the
observation period). Many State
agencies use these latter techniques,
and have adopted their methods in
their SIP rules and regulations. EPA V£ Determination
currently has studies underway to '• Position
evaluate 'the accuracy and'reliability of
these nonaveraging techniques.



2. Observations
'


3. Field data: VE
observation form



4. Facility operating
data


Special observation
problems




Completed per-
imeter survey



Observer should
follow protocol
as suggested in
Subsec 4.2 and
adhere to con-
fidentiality of
data



In accordance
with Subsec
4.3.1



Token in accord-
ance with Sub-
sec 4.3. 1

Completed data
form



Pertinent pro-
cess data
obtained

N/A





Prior to. follow-
ing, and during
(if warranted)
the VE deter-
mination
Entry prior to
taking VE read-
ings only if
necessary; entry
after VE readings
to provide plant
representative
with data and/or
to obtain neces-
sary plant pro-
cess data

Take a position
for observation
as described in
Subsec 4.3. 1
and document
on data form

Make VE deter-
mination as
described in
Subsec 4.3. J
Complete data
form as per in-
structions and
examples in
Subsec 4.3.2
After VE obser-
vations, obtain
facility data per
Subsec 4.3.3
Refer to Subsec
4.4 when condi-
tions do not per-
mit VE observa-
tion under pro-
per position, etc.
N/A



N/A





Follow instruc-
tions under
special probtems
(Subsec 4.4)
when a proper
position cannot
be assumed
As above



Complete miss-
ing data (if
possible) or give
rationale for in-
complete dsta
Data must be
obtained as soon
as possible after
VE observation
N/A





                                                                                         o
                                                                                          o
              N/A = not applicable.
                                                                        -\
                                                                                           O

-------
                            April 1983
                                                                         Section 3.12.5
                                 5.0   Postobservation Operations
     Table 5.1 at the end of this section
   summarizes the quality assurance
   activities for postobservation
   operations. These activities include
   preparation of reports and  data
   summaries and validation.

   5.1   Data Summary
     The opacity observations are
   recorded on data forms such as those
   shown in Figures 4.1 and 4.2. Figure
   5.1 is a summary data form for
   manual calculations. This form and
   the calculation procedures  are
   discussed in detail in Section 3.12.6.
   It is recommended, however, that a
   computer be used when reducing

   Company  AJ/nfral foutr Hdt\f
   Start time    /33O	Emission point
                                      large quantities of data and to avoid
                                      calculation errors.

                                      5.2  Reporting Procedures
                                        Recording opacity observation data
                                      on a three-part form is most
                                      convenient. One part can be given to
                                      the appropriate facility personnel
                                      immediately following the on-site field
                                      observation if this is the agency policy
                                      or procedure,  one part should be
                                      given to the Agency, and one part
                                      should be maintained in the
                                      observer's file. The data form should
                                      be completed  on-site, and it should be
                                      signed by the  observer, the facility
                                      representative {if applicable),  and the
                                           /5
                                                                           data validator. All corrections mure be
                                                                           initialed. The file copy should be
                                                                           signed by the data validator.
                                                                             Inspection forms alone may not be
                                                                           adequate for documenting an
                                                                           enforceable violation and can be
                                                                           supplemented by a narrative report. It
                                                                           is recommended that a summary
                                                                           report be made containing the
                                                                           following information:

                                                                             1 . Name and location of facility,
                                                                               date and time of inspection,
                                                                               name of inspector, and name of
                                                                               company official(s) contacted.
                                                                             2. Brief  description of the specific
                                                                               process information gathered.
                                           Ft'ftd 'Boiler
                                                                         . Location .
Stan
no.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
Total
opacity
sts
860
vto
MS










Average
opacity
at'fe
950
35.2.










Stan
no.
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
Total
opacity












Average
opacity












Stan
no.
73,
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
T01
102
1O3
104
105
106
107
108
Total
opacity












Average
opacity












Stan
no.
109
no
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
Total
opacity












Average
opacity












Start
no.
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
16O
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
Total
opacity












Average
opacity












Start
no.
181
182
183
184
185
186
187
188
189
190
191
192
193
194
195
196
197
198
199
20O
2O1
202
203
204
205
2O6
2O7
2O8
209
210
211
212
213
214
215
216
Total
opacity



Average
opacity




i
i
i












Maximum average
iljl Number of nonoverlappit

-------
                        Section 3.12.5
                                                                          April 1983
     particularly any unusual
     occurrences.
  3. Description of the equipment that
     was inspected and its operating
     mode at the time of inspection.
  4. Notation of any  excessive
     emissions seen  and
     corresponding data from opacity
     continuous emissions monitor if
     available.
  5. Explanation of excessive
     emissions,  if available, and
     corrective actions being taken.
  6. Summary of emission points not
     in compliance.
  7. Recommendations for followup
     action.
  One copy of the  report, an updated
plot plan, photographs, and other
pertinent data should be placed in the
Agency file. Whenever a violation is
noted, it is EPA policy to notify the
facility of the alleged violation and to
permit them to review the evidence
against  them in  a meaningful way.
The importance of  a good file cannot
be overstated. This file represents the
official Agency documentation of
compliance history, the latest
information on the source's operation
and compliance  status. The file also
provides the means of communicating
source conditions to other staff
members. A thorough and accurate
historical record on source inspections
and opacity readings is essential to
good operation and any necessary
compliance/enforcement actions.
5.3  Data Validation
  All opacity observation data
obtained for compliance determination
should be validated by senior staff
assigned this responsibility. Data
validation procedures are described in
References 16 and 17. These data
should be checked to the extent
possible for their completeness, the
correctness of source, the emission
point and description, the background,
and the  process and control
equipment in use. The calculation of
the average opacities and highest
average opacity also should be
checked. All calculation checks should
agree within acceptable roundoff
errors. If possible, any questionable
data should be reviewed with the
observer. Ideally the data validation
should occur as soon as possible after
the observations are recorded so that
questions may be resolved. Any other
calculations made for the purpose of
supporting the data (e.g., the effect  of
angle of observation on the observed
opacity)  should also be verified. Note:
Any corrections in the data  must be
forwarded to all interested parties so
that they may correct their records (a
data form should have been given to
them after the opacity observations
were completed).

5.4  Equipment  Check
  A check of the equipment following
the opacity observations helps to
ensure the quality of the data. Any
indication of equipment
damage/malfunction should be
recorded on an equipment log and
noted for purposes of data validation.
The malfunctioning equipment should
be repaired, adjusted, or replaced so
that the equipment will be available
for subsequent on-site field
observations.
o
                                    o
Table 5.1.     Activity Matrix for Postobservation Operations
A ctivity
Data summary



Reporting procedures




Data validation





Equipment check







Acceptance
limits
Completed data
form


Completed re-
port and data
forms


All checks
should agree
within accept-
able roundoff
error

All equipment/
apparatus
should be
checked for sat-
isfactory opera-
tion after each
VE observation
day
Frequency and
method of
measurement
See Subsec
3.12.6 for in-
structions for
calculations
Use 3-part form
as suggested in
Subsec 5.2


Make data valid-
ation check as
soon as possible
after VE obser-
vation

Check equip-
ment for
damage/mal-
functions




Action if
requirements
are not met
Complete the
data summary


Complete the
necessary data
forms and re-
porting proce-
dure
Forward all
corrections of
the data/calcul-
ations to the
interested
parties
Note on equip-
ment log and
repair, adjust or
replace the
equipment



                                                                                                                O

-------
                            April 1983
                                                                          Section 3.12.6
  Three types of calculations are
described in this section: (1) the
calculation of the average opacity for
the specified time period (usually 6
min, or 24 observations recorded at
15-s intervals), (2) the calculation of
the path  length through the plume
(seldom needed), and (3) the
prediction of steam plume formation
(seldom needed). In the first
calculation, the 6-min running (or
rolling) averages may be required. To
minimize errors in the calculations,
another individual should check all
calculations for each VE
determination for compliance. If a
difference greater than a typical
roundoff error is detected, the
corrections should be made and
initialed by the one making the
correction. Table 6.3 at the end of this
section summarizes the quality
assurance activities for these
calculations.

6.1   Calculation of Average
Opacity
  Figure  6.1 shows actual opacity
data taken at one company
(unspecified) for two 6-min periods.
Note: Any corrections made by an
observer  must be initialed and the
corrected value used in the
computation of an average. The
calculations can be checked by
obtaining the row and column
subtotals; the totals of these subtotals
must be identical.
  Running 6-min averages are
calculated from data on  Figure 6.2
and reported as described below.
Running  averages can include a time-
lapse break in opacity readings when
caused by an element that makes taking
a valid reading difficult (e.g., fugitive
emissions, improper background, or
process shutdown). Running averages
should not contain time-lapse breaks
in the readings as a result of the
observer's desire not to take visible
emission data for personnel reasons
when conditions exist that would
allow the observer to take valid
opacity data (e.g., eye strain or no
desire to  continue readings).  Figure
6.3 is included to provide an  easy
reference between the VE reading
time on Figure 6.1 and the start
number on Figure 6.2. The start
numbers are used to find the
corresponding observation time for
the beginning of the calculated six
minute average.
      6.0  Calculations

  Determination of the running
average is generally performed by
computer or by a hand calculator. The
main purpose of the calculations is to
determine the number of 6-min
periods in excess of the standard and
the greatest value for any 6-min
period. It is also suggested, but not
required, that the opacity readings be
plotted on a graph showing percent
opacity versus time, with a straight
line connecting each subsequent
reading.

6.1.1  Use of Computer for
Calculations - It is highly
recommended that a computer be
used to calculate and plot data.
Programming will vary with the
language used by the particular
computer, but the basic principle is as
follows:  ,..
Input:    r
  1. Enter, all VE readings with their
   .  corresponding  start number or
     identifying start time.
Computation:
  1. The first average opacity reading
     is obtained by averaging the first
     24 opacity readings.
  2. Each succeeding running
     average is obtained from the
     previous one by adding the next
     observation reading and
     subtracting the first observation
     in the series and then dividing by
     24 (assuming 6-min running
     average).
Printout
  1. The computer should print all VE
     readings with their
     corresponding number or time.
     This printing will ensure that all
     readings have  been entered
     properly.
  2. The computer should search all
     averages and print the highest
     average opacity and its
     corresponding number or time
     interval.
  3. Starting at the first interval, the
     computer should search for all
     nonoverlapping 6-minute periods
     in excess of the standard. Each
     interval's average opacity value
     and corresponding number or
     time should be printed out.
  4. Finally the computer should plot
     VE readings versus time
     intervals. If the computer has a
     plotter, it should be used, tf not,
     the values can be plotted without
     connecting lines. If desired, the
     computer can bracket intervals in
     excess of the standard.

 6.1.2  Use of Hand Calculator for
 Calculations - When a hand calculator
 is used, the calculation procedures
 are the same as those for the
 computer, except that they must be
 performed manually. All data should
 be recorded on the VE Summary Data
 Sheet (see Figure 6.2) if desired. To
 avoid calculating average opacity
 values that are less than the standard.
 the following procedure can be used.
 The total value for the 24 readings
 should be calculated first, and the
 total opacity should be entered at
 Start no. 1.
   Each succeeding total value can be
 obtained and recorded by addirxj the
 difference between the value dropped
 and the one added. These calculations
 can be performed easily without a
 calculator.  If desired, the average
 opacity reading could then be
 calculated only for those totals that
 exceed the total allowable opacity
 limit (e.g., 20% x 24 = 480). Therefore,
 a total opacity of 480 or greater would
 be an exceedance of a 20 percent
 opacity standard. Method 9 does,
 however, require that the accuracy of
 the method be taken into account
 when determining possible violations
 of applicable opacity standard.
   It is suggested that when the
 opacity standard has been exceeded
 for any 24 consecutive readings, the
 data be hand-plotted with each VE
 reading versus its time interval. These
 plots fit best on graph paper scaled 1O
 lines to the inch. Each 15-second
 reading can be plotted at 1/2 spacing.
 thereby allowing 2O readings per  inch.
 If desired, intervals of opacity in
 excess of the standards can be
 marked on this plot. It is much easier
 to visualize a trend in opacity with
 time with such a graphical
 presentation than with tabulated
 numerical readings as shown in
 Figure 6.4.

 6.2   Calculation of Path
 Length Through the Plume
  The  observer should be located so
that only one plume diameter is being
sighted through. In rare cases, the
observer has no choice but to be
relatively close to the stack so that the
view is up through the plume rather
than across it. In these cases, this
extra width of plume should be
                                                                                           7

-------
                           Section 3.12.6
                                                                                  April 1983

SOURCE NAME
APAl/flAL POUZ& PLAIJT
ADDRESS
///t OC£J\fiJ /^OAO

CITY
ADMW
.at/
PHONE
STATE
VA
ZIP
SOURCE ID NUMBER
/V£P5 457M
PROCESS EQUIPMENT
CONTROL EQUIPMENT
OPERA TING MODE
*T^< A-^i/^ / ^\ A T*^
f^f^^J^^ f-~^Jf\J-^
OPERA TING MODE
Rhfriti ' STOP t^
DISTANCE FROM OBSERVER
START J/OQ' STOP)/
HEIGHT RELATIVE TOOBSERVER
START /OO ' STOP ^
DIRECTION FROM OBSERVER
START /WE- STOP ^/^
DESCRIBE EMISSIONS p/jtMEL
START STOP |xx'~~
EMISSION COLOR
WATER DROPLETS PRESENT:
NO Of YESO
PLUME TYPE: CONTINUOUS ef
FUGITIVE D INTERMITTENT D
IF WATER DROPLET PLUME:
ATTACHED D DETACHED O
POINT IN THE PLUME A T WHICH OPACITY WAS DETERMINED
START /o'AS&je. -snU!>S
SKY CONDITIONS f/^KTL^
START CV£AR-STOPCUWI>Y
WIND DIRECTION
/
START ^>^ STOP iX
WET BU
Source Layout Sketch
A*
"

H



\ — \ — \ — \ — \ —
	 . /*
KAfJT
Su

^
Plu
Sta
Y. •
/
Wind^
me and — ^^J±,
:k ^^--^C
^<*^X-±14C

LB
TEMP.
•^
Draw North A
7KACKS /•


ii
\ 	 \ — \ 	 1 	 I-^O
\Efnission Point
ft
Observers Position
0 ^^^**^ u '


Sun Location Line~
0

RH.percent
rrow
7)
' 	 s
teH
3rtD
— «•
•~
e//ce

COMMENTS .£/.
L/ses ^ OIL

1 HAVE RECEIVED A COPY OF THESE OPACITY OBSERVATIONS
SIGNATURE t(/M&a4r\. ?? §OL***JL
TITLE "
5H/FT MAfJAC}£&.
DATE
OBSERVATION ZATE
yww\
7
2
3
4
5
6
7
8
S
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
0
30
55
35
30
•5
35
3d
35
35
50 3*
35
30
35
35
30
40
60 ^5
50
45
30 SO
30
30
30
55
fo
35
35
30
35
35
60
55
35
30
30
•






i







i
1
























START TIME
/330
45
55
30
3S
35
^0
35
35
55
60
30
-30
30


















A VERA GE OPA CITY FOR /
HIGHEST PERIOD ^O /O
\SfC
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
STOP TIME
0 75






I






























I














30












45















































NUMBER OF READINGS ABOVE
^O % WERE /(
RANGE OF OPACITY READINGS -+ //"SO/
MINIMUM 3
DATE
                                                                                                                              o
                                                                                                                             o
                                                                                                                             o
Figure 6,1.    Visible emission observation form.

-------
                               April 1983
                                                                               Section 3.12.6
                                           Visible Emission Summary Data Sheet
 Company

 Sfart f/me
                                                                              .Location
                            Emission point
                                                F)f?£T>
Start
no.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
Total
opacity
essr
4&o
&(,0
£2fsQ
&(J {%*






























Average
opacity
2&-B
36%
2£g
3i££>
2&2-






























Start
no.
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
Total
opacity



































Average
opacity



































Start
no.
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87-
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104,
105
106
107
108
Total
opacity



































A verage
opacity



































Start
no.
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
Total
opacity



































A verage
opacity



































Start
no.
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
Total
opacity



































Average
.opacity



































Stan
no.
181
182
183
184
185
186
187
188
189
190
191
192
193
194
195
196
197
198
199
200
201
202
203
204
205
206
207
208
209
210
211
212
213
214
215
216
Total
opacity



































Average
opacity



































                                    . % Start number of
Maximum average
Number of nonoverteppina averaoesifi excess of standard _i
r.atmiaterihy  {/.&,P&6FP&T	Dale^
Calculated by

Figure 6.2.   Visible emission summary data sheet.
p/x minute average  / /	
     Listing start number of these averages
                                                                                                   VO_.l /S.—

-------
                          Section 3.12.6
                                                                            April 1983
                                       VISIBLE EMISSION OBSERVATION FORM
SOURCE NAME
ADDRESS

CITY
PHONE
STATE
ZIP
SOURCE ID NUMBER
PROCESS EQUIPMENT
CONTROL EQUIPMENT
DESCRIBE EMISSION POINT
START STOP
HEIGHT ABOVE GROUND LEVEL
START STOP
DISTANCE FROM OBSERVER
START STOP
HEIGHT
START
OPERATING MODE
OPERATING MODE

RE LA TIVE TO OBSER VER
STOP
DIRECTION FROM OBSERVER
START STOP
DESCRIBE EMISSIONS
START STOP
EMISSION COLOR
START STOP
WATER DROPLETS PRESENT:
NO D YE SO
PLUME
FUGITIV
TYPE: CONTINUOUS D
ED INTERMITTENT D
IF WA TER DROPLET PLUME:
ATTACHED D DETACHED D
POINT IN THE PLUME A T WHICH OPA CITY WAS DETERMINED
START STOP
DESCRIBE BACKGROUND
START STOP
BACKGROUND COLOR
START STOP
WIND SPEED
START STOP
AMBIENT TEMP.
START STOP
Source Layout Sketch
X
Sun-fy Wind.*.
Plume and ~ ^^
Stack ^^^\
^^^^ ^141.
SKY CONDITIONS
START STOP
WIND D
START
IRECTION
STOP
WET BULB TEMP. RH.percent


Draw North Arrow

( . J
^-^
Emission Point


Observers Position

>-^
Sun Location Line
COMMENTS

1 HAVE RECEIVED A COPY OF THESE OPACITY OBSERVATIONS
SIGNATURE
TITLE
DATE
OBSERVATION DATE
/VfW\
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
*
23
24
25
26
27
28
23
30
0
1
5
9
13
17
21
25
29
33
37
41
45
49
53
57
61
65
69
73
77
81
85
89
93
97
101
105
109
113
117
15
2
6
10
14
18
22
26
30
34
38
42
46
50
54
58
62
66
70
74
78
82
86
90
94
30
3
7
11
15
19
23
27
31
35
39
43
47
51
55
59
63
67
71
75
79
83
87
91
95
9S '. 99
102
106
110
114
118
103
107
111
115
119
START TIME
45
4
8
12
16
20
24
28
32
36
40
44
48
52
56
60
64
68
72
76
80
84
88
92
96
100
104
108
112
116
120
A VEFtA GE OPACITY FOR
HIGHEST PERIOD
\S£C
MIN\
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
.57
58
59
60
0
121
125
129
133
137
141
145
149
153
157
161
165
169
173
177
181
185
189
193
197
201
205
209
213
217
221
225
229
233
237
STOP TIME
15
122
126
130
134
133
142
146
ISO
154
158
162
166
170
174
178
182
186
190
194
198
2O2
2O6
21O
214
218
222
226
230
234
238
30
123
127
131
135
139
143
147
151
155
159
163
167
171
175
179
183
187
191
195
199
203
207
211
215
219
223
227
231
235
239
45
124
128
132
136
140
144
148
152
156
160
164
168
172
176
180
184
188
192
196
200
204
208
212
216
220
224
228
232
236
24O
NUMBER OF READINGS ABOVE
% WERE
RANGE OF OPACITY READINGS
MINIMUM MAXIMUM
OBSERVER'S NAME (PRINT)
OBSERVER'S SIGNATURE
DATE
ORGANIZATION
CERTIFIED BY
VERIFIED BY
DATE
DATE
                                                                                                                 3
                                                                                                                 D
                                                                                                                 D
Figure 6.3.    Opacity data form with start numbers shown.

-------
                            April 1983
                                    Section 3.12.6
     30
     20

     10
                                                                           the known height of the stack and the
                                                                           distance from the observer to the base
                                                                           of the stack.
                                                                           Method 1 (when slant angle 8 is known)
                                                 1 -(
                                                                                          100
                                                                                               = T0Equation 6-1
                               Time, minutes
Figure 6.4.   Plot opacity versus time.

acknowledged and the individual data
values may be adjusted
mathematically in the final data report
to show the increase in opacity
reading due to the added path length.
These adjusted opacity readings
should be used in determining
averages in excess of the standard.
  The calculation of  observed  path
length is shown in Appendix A of
Reference 1 and  is included here for
the observer's convenience. Figure
6.5 shows how the slant angle varies
with distance from an elevated
source. As an observer moves closer
to the base of the stack, the angle of
sight and the path length through the
plume both increase; this causes the
observed opacity to increase even
though the cross-plume opacity
remains constant. This situation only
applies when the opacity is read
through a vertically rising plume and
the observer is on the same plane as
the base of the stack.
  The actual opacity may be
calculated from the observed opacity,
if the slant angle 6 is known, or from
         (1  -T£)x 100 = 0c
where
  O0= observed opacity in %
  T0= observed transmittance
   F= cosine of 6
  Oc= corrected opacity in %.
Method 2 (where distances are known)
       Y
         Y2             Equation 6-2
           1-< Op ) = T0
               100
         (1  -To)x 100 = 0C

where
  00r observed opacity in %
  To = observed transmittance '    ,
   F= cosine of 6
  Oc= corrected opacity in %
  H= height of stack
  Y= distance of observer from stack.
  Note: Since the correction is a
power function, the correction must
be made on each opacity reading and
the corrected values used for
calculations, in lieu of the correction
being conducted on the reduced
(averaged) data.
  Table 6.1 presents the opacity
corrected for slant angle or viewing
angle 6 versus the full range of
opacity readings. For angles less than
approximately 18° the adjustment is
relatively insignificant.
6.3   Predicting Steam  Plume
Formation
  The psychrometric chart can be
used in conjunction with a simple
    	Par/) Length through Plume
Figure 6.5.    Variation of observation angle and pathlength with distance from an elevated source.
                                                                                      ,l«f
-------
                         Section 3.12.6
                                    April 1983
Table 6. 1 . Opacity Correction for Slant Angle
Measured
opacity. Slant anale 8, dearees
% 0 10 20
95 95 95 94
90 90 90 89
85 85 85 83
80 80 80 78
75 75 75 73
70 70 70 68
65 65 64 63
60 60 59 58
55 55 55 53
50 50 50 48
45 45 45 43
40 40 40 38
35 35 35 33
30 30 30 29
25 25 25 24
20 20 -20 19
15 15 15 14
10 10 10 9
5 554
0 000
equation to predict the formation of a
visible water vapor (steam) plume. The
psychrometric chart is a graphical
representation of the solutions of
various equations of the state of air
and water vapor mixtures (see Figure
6.6). Both the ambient and stack
emission data points on the chart are
referred to as their "state point" and
represent one unique combination of
the following five atmospheric
Dronerties.
3O 40 50 60
93 90 85 78
86 83 77 68
81 77 71 62
75 71 65 55
70 65 59 50
65 60 54 45
60 55 49 41
55 50 45 37
50 46 40 33
45 41 36 29
40 37 32 26
36 32 28 23
31 28 24 19
27 24 21 16
22 20 17 13
18 16 13 11
13 12 10 8
9875
4333
0000
represented by the set of curved lines
originating in the lower left portion of
the chart.
Absolute humidity (humidity ratio) -
The mass of water vapor per unit
mass of air; expressed as grains per
pound or pound per pound;
represented by the vertical axes.
Specific volume - The volume
occupied by a unit mass of air,
expressed as cubic feet per pound,
determines the values for the
remaining three properties. For
example, by using a sling
psychrometer to measure the we: and
dry bulb temperatures, one can
determine the relative humidity, the
absolute humidity, and the specific
volume of the air.
To predict the occurrence of a
visible steam plume, both the amt>ent
air conditions and the stack gas
conditions must be known or
calculated and located on the
psychrometric chart. If any portion of
the line connecting the two points lies
to the left of the 100 percent relatrve
humidity line, it is an indication that
the change of the exhaust gas from
the stack state conditions to the
ambient air state will be accompanied
by the condensation of the water
vapor present in the exhaust stream
and a resultant visible steam plume.
Obtaining the state point for the
ambient air conditions is relatively
simple; as previously indicated, the
wet and dry bulb temperatures, which
will determine a unique state point
can be measured by using a sling
psychrometer. Often the only data
available for determining the state
point of the stack gas are the dry bulb
temperature of the exhaust gas
stream and its moisture content.*
However, a relationship exists
between the moisture content and the
humidity ratio (or absolute humidrty},
as shown in the following equation:
 Dry bulb temperature - The actual
 ambient temperature; represented by
 the horizontal axis.
 Wet bulb temperature - The
 temperature indicated by a "wet bulb"
 thermometer ( a regular thermometer
 that has its bulb covered with a wet
 wick and exposed to a moving air
 stream); represented by the curved
 axis on the left side of the chart
 (saturation temperature).
 Relative humidity - The ratio of  the
 partial pressure of the water vapor to
 the vapor pressure of water at the
 same temperature; values are
represented by the diagonal lines
running from lower right to upper left.
The relationships shown in the chart
differ with changes in barometric
pressure. The chart included in this
section is for a barometric pressure of
29.92 inches of mercury. Therefore,
with use of wet bulb dry bulb
technique, if the actual pressure is
less than about 29.5 inches of
mercury, the humidity ratio should be
calculated from the equation and not
the chart.

  Plotting the values for any two of
the five atmospheric properties
                 - MC
                         Equation 6-3
Table 6.2.    Vapor Pressures of Water at Saturation
Temp.,
°F
30
40
50
60
70
SO
90
100
110
120
130

0
0. 1647
0.2478
0.3626
0.5218
0.7392
1.032
1.422
1.932
2.596
3.446
4.525

1
0.1716
0.2576
0.3764
0.5407
0.7648
1.066
1.467
1.992
2.672
3.543
4.647

2
0.1803
0.2677
0.3906
0.5601
0.7912
1.102
1.513
2.052
2.749
3.642
4.772
Water
3
0. 1878
0.2783
0.4052
0.5802
0.8183
1.138
1.561
2.114
2.829
3.744
4.900
vapor pressure.
4
0. 1955
0.2891
0.4203
0.6009
O.8462
1.175
1.610
2.178
2.911
3.848
5.031
5
0.2035
0.3004
0.4359
0.6222
0.8750
1.213
1.660
2.243
2.995
3.954
5.165
in. Hq
6
0.2)18
0.3120
O.4520
0.6442
0.9046
1.253
1.712
2.310
3.081
4.063
5.302

7
0.2203
0.3240
0.4586
0.6669
0.9352
1.293
1.765
2.379
3.169
4.174
5.442

8
0.2292
0.3364
0.4858
0.6903
0.9666
1.335
1.819
2.449
3.259
4.289
5.585

9
0.2383
0.3493
0.5035
0.7144
0.9989
1.378
1.875
2.521
3.351
4.406
5.732
where
HR = humidrty ratio, in pound of water
     vapor per pound of dry air
MC = — %_ moisture content, expressed
     100
     as a decimal.
The following sample problem
demonstrates the use of this
equation.
Given:
  Ambient conditions
    Dry bulb temperature = 70°F
    Wet bulb temperature = 60°F
    Barometric pressure = 29.92 in. Hg
  Effluent gas conditions
    Dry bulb temperature = 1 60°F
    Moisture content = 16.8% = 0.1 68
                     1OO
Find:
  Ambient relative humidity
  Exhaust gas humidity ratio
  Determine whether or not
  condensed water (steam plume)
  will form
                                                                                                                  o
                                                                                                                  o
                                                                                                                  o
                                                                            'These are usually obtained from plant recons
                                                                            or are estimated from recent source test data

-------
                            April 1983
                                                   Section 3.12.6
 Solution:
   Plot ambient wet bulb and dry bulb
   temperatures (see Figure 6.5).
   Ambient relative humidity = 55%.
   Exhaust gas humidity ratio = HR
     HR=0.62(MC)
          1 - MC
        =0.62(0.168)
          1 -0.168
        =0.125 Ib/lbdryair
 Plot humidity ratio and stack dry bulb
 temperature (see Figure 6.6). Connect
 the ambient state point and stack gas
 state point with a straight line (see
 Figure 6.5). The line crosses the 100
 percent relative humidity line; thus,
 formation of a visible water vapor
 plume is probable.
  When the wet bulb/dry bulb
 technique is used and the barometric
 pressure is less than 29.5 in. Hg, it is
 suggested that Equation 6-5 be  used
 to calculate the moisture content
 (MC).
               where
                VP = Vapor pressure of HzO using
                    Equation 6-6
               Pabs = Barometric pressure
VP = SVP - (3.57x10"")
    (1 +Tw - 32)
         1571
                                          (Td-Tw)
                                      Equation 6-6
where
SVP = Saturated vapor pressure in in.
      Hg at wet bulb temperature
      (taken from Table 6.2)
  Td = Temperature of dry bulb
      thermometer, °F
  Tw = Temperature of wet bulb
      thermometer, °F.
              Table 6.3    Activity Matrix for Calculations
              Calculation
                     Acceptance
                     limits
  Frequency and
  method of
  measurement
Action if
requirements
are not met
              Average opacity
      Pab
Equation 6-5
              Running average
              opacity

              Path length through
              the plume
                                      Predicting steam
                                      plume
                     Data in Fig 6.1
                     completed and
                     checked to with-
                     in roundoff error
                     Data in Fig 6.2
                     completed and
                     checked
                     No limits have
                     been set
                                    No limits have
                                    been set
  For each com-
  pliance test.
  perform inde-
  pendent check
  of data form and
  calculations
  As above
  For each com-
  pliance test with
  the slant angle
  >J8°. calculate
  using Eq. 6-1
  Use psychro-
  metric chart and
  Equation 6-3
Complete the
data and initial
any changes in
calculations
As above
Perform calcu-
lations
                                                          Perform calcu-
                                                          lations
                                                                                                         0.14
                                      u
      _ Psychrometric Chart              iTwi-f
       Barometric Pressure 29.92 Inches of Mercur
                                      <:
                                               ; gg^jESg^ffisSISruS
                                               jS^rrtTgg^t! ryirtsLv jr-Tl^;
        46
    O - State Point for Ambient Conditions.
    Q - State Point for Stack Gas Conditions.
                140    160   180    200   220    240   260

                     Dry Bulb Temperature. °F
                                                                                      280   300
                                                                                                   320
Figure 6.6.    Psychrometric chart for problem solution.

-------
o
o
o

-------
                            April 1983
                                    Section 3.12.7
  An audit is an independent
assessment of data quality.
Independence is achieved by using
observers and data analysts other
than the original observer/analyst.
Routine QA checks for proper
observer positioning and
documentation are necessary to
obtain good quality data. Table 7.1 at
the end of this section summarizes
the QA activities for auditing.
  Two performance audits are
recommended for VE readings:
  1. Audit of observer by having an
     experienced observer make
     independent readings.
  2. Audit of data forms and
     calculations.
In addition, it is recommended that a
systems audit be conducted by an
experienced observer at the same
time the performance audit of visible
emissions is conducted. The two
performance audits are described in
Subsection 7.1 and the systems audit
is described in Subsection 7.2.

7.1  Performance Audits
  Performance audits are quantitative
evaluations of the quality of visible
emission data.

7.1.1  Performance Audit of Visible
Emissions -  In this audit, an
experienced observer goes with the
observer being audited and both
observers take the readings
simultaneously (using the same time
piece) and complete the data forms as
independently as is practical. The
audit is intended for observers in their
first year and observers who have not
made opacity observation in the field
in over a year. The differences
between the two readings serve as a
measure of accuracy assuming the
experienced observer reads the "true
opacity." Because this assumption is
not necessarily correct, the difference
between the two readings is a
combined measure of accuracy of
both observers. For a minimum of six
minutes (24 readings), the average of
the absolute differences should be less
than iO percent, and no individual
differences should exceed 20 percent.
(The values of 10% and 20%
suggested for the limits are the
approximate results of combining the
allowable errors of the two observers;
e g.,V(7.5)2 + (7.5J2 = 10.6%, and
V152 + 152 = 21.2%. This audit should
be performed twice in a year for the
7.0   Auditing Procedures

first year of an observer and
whenever conditions tend to warrant
them thereafter. Calculate %A using
Equation 7-1.
   %A = |VE (observer) - VE (auditor)!
                       Equation 7-1
where
   VE (observer)=average and in-
                dividual VE
                reading(s) of the
                observer being
                audited
    VE(auditor) = average and
                individual VE
                reading(s) of the
                auditor.

7.1.2  Performance Audit of Data
Calculations - This audit is an
independent check of all calculations
performed for the summary VE report.
Every calculation should be checked
within round-off error. This audit
should be conducted on at least 7
percent of the annual numbers of VE
summary reports.

7.2  System Audit
  A system audit provides an on-site
qualitative inspection and review of
the total inspection. This audit
includes a check of the  "Record of
Visual Determination of Opacity,"
Figure 9.1 of Section 3.12.8, and the
top portion of the "Observation
Table 7.1.    A ctivity Matrix for A uditing Procedures
Record," Figure 9.2 of Section 3.12.8.
In addition, the auditor should assess
the visible emission inspection
technique used by the auditee. This
portion of the system audit is best
handled in conjunction with the
performance audit described in the
previous Subsection 7.1.1. Therefore,
the frequency of the system audit
should coincide with the frequency of
the performance audits of visible
emissions. Some observations to be
made by the auditor are listed in
Figure 7.1.
Audit
Performance audit
of visible emissions




Performance audit
of data calculations




System audit






Acceptance
limits
Individual obser-
vations within
±20%; average
(absolute) devia -
tion within
±10%
Original and
check calcula-
tions agree
within round-off
error

Conduct obser-
vations as de-
scribed in this
section of
the Handbook


Frequency and
method of
measurement
At least two
times during the
first year: sim-
ultaneous ob-
servation and
data recording
Seven percent
of tests for
compliance, per-
form indepen-
dent check on
all calculations
At least two
times during the
first year; use
audit checklist
(Fig 7.1 )


Action if
requirements
are not met
Review obser-
vation tech-
niques



Check and cor-
rect all calcu-
lated results
(averages]


Explain to obser-
ver the devia-
tions from rec-
ommended
procedures;
note the devia-
tions on Fig 7. 1

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-------
                            April 1983
                                                                          Section 3.12.8
Method 9—Visual
Determination of the Opacity
of Emissions from  Stationary
Sources
  Many stationary sources discharge
visible emissions into the atmosphere;
these emissions are usually in the
shape of a plume. This method
involves the determination of plume
opacity by qualified observers. The
method includes procedures for the
training and certification of observers,
and procedures to be used in the field
for determination of plume opacity.
The appearance of a plume as viewed
by an observer depends upon a
number of variables, some of which
may be controllable and s'ome of
which may not be controllable in  the
field. Variables which can be
controlled to an extent to which they
no longer exert  a significant influence
upon plume appearance include:
Angle of the observer with respect to
the plume; angle of the observer with
respect to the sun; point of
observation of attached and detached
steam plume; and angle of the
observer with respect to a plume
emitted from a rectangular stack with
a large length to width ratio. The
method includes specific criteria
applicable to these variables.
  Other variables which may
not be controllable in the field are
luminescence and color contrast
between the plume and the
background against which the plume
is viewed. These variables exert an
influence upon the appearance of a
plume as viewed by an observer,  and
can affect the ability of the observer
to accurately assign opacity values to
the observed plume. Studies of the
theory of plume opacity and field
studies have demonstrated that a
ptume is most visible and presents the
greatest apparent opacity when
viewed against a contrasting
background. It follows from this, and
is confirmed by field trials, that the
opacity of a plume, viewed under
conditions where a contrasting
background is present can be
assigned with the greatest degree of
accuracy. "However, the potential  for a
positive error is also the greatest
when a plume is viewed under such
contrasting conditions. Under
conditions presenting a less
contrasting background, the apparent
opacity of a plume is less and
 8.0   Reference  Method8

 approaches zero as the color and
 luminescence contrast decrease
 toward zero. As a result, significant
 negative bias and negative errors can
 be made when a plume is viewed
 under less contrasting conditions. A
 negative bias decreases rather than
 increases the possibility that a plant
 operator will be cited for a violation of
 opacity standards due to observer
 error.
   Studies have been undertaken to
 determine the magnitude of positive
 errors which can be made by qualified
 observers while reading plumes under
 contrasting conditions and using the
 procedures set forth in this method.
 The results of these studies (field
 trials) w-hich involve a total of 769
 sets of 25 readings each are as
 follows:

  (1)  For black plumes (133 sets at a
      smoke generator). 100 percent
   '   of the  sets were read with a
      positive error1 of less than 7.5
      percent opacity; 99 percent
      were read with a positive error
      of less than 5 percent opacity.
  (2)  For white plumes (170 sets at a
      smoke generator, 168 sets at a
      coat-fired power plant, 298 sets
      at a sulfuric acid plant), 99
      percent of the sets were read
      with a positive error of less than
      7.5 percent opacity; 95 percent
      were read with a positive error
      of less than 5 percent opacity.
  The positive  observational error
associated with an average of twenty-
five readings is therefore established.
The accuracy of the method must be
taken into account when determining
possible violations of applicable
opacity standards.

1.   Principle and applicability.

 /. 7   Principle. The opacity of
emissions from stationary sources is
determined visually by a qualified
observer.

 1.2   Applicability. This method is
applicable for the determination of the
opacity of emissions from stationary
sources pursuant to § 60.11(b) and for
qualifying observers for visually
determining opacity of emissions.
'For a set positive error = average opacity
determined by observers' 25 observations —
average opacity determined from
transmissometer's 25 recordings.
2.  Procedures.
   The observer qualified in
accordance with paragraph 3 of this
method shall use the following
procedures for visually determining
the opacity of emissions:

2.1  Position. The qualified observer
shall stand at a distance sufficient to
provide a clear view of the emissions
with the sun oriented in the  140°
sector to his back. Consistent with
maintaining the above requirement,
the observer shall, as much as
possible, make his observations from
a position such that his  line of vision
is approximately perpendicular to the
plume direction, and when observing
opacity of emissions from rectangular
outlets (e.g. roof monitors, open
baghouses, noncircular stacks),
approximately perpendicular to the
longer axis of the outlet. The
observer's line of  sight should not
include more than one plume at a
time when multiple stacks are
involved, and in any case the observer
should make his observations with his
line of sight perpendicular to the
longer axis of such a set of multiple
stacks (e.g. stub-stacks on
baghouses).

2.2  Field records. The observer
shall record the name of the plant,
emission location, type facility,
observer's name and affiliation, and
the date on a field data sheet (Figure
9-1). The time, estimated distance to
the emission location, approximate
wind direction, estimated wind speed.
description of the  sky condition
(presence and color of clouds), and
plume background are recorded on a
field data sheet at the time opacity
readings are initiated and completed.

2.3  Observations. Opacity
observations shall  be made at the point
of greatest opacity in that portion of
the plume where condensed water
vapor is not present. The observer
shall not look continuously at the
plume, but instead shall observe the
plume momentarily at 15-second
intervals.

2.3.1. Attached steam plumes. When
condensed water vapor is present
within the plume as it emerges from
the emission outlet, opacity
observations shall be made beyond the
point in the plume at which

-------
                          Section 3.12.8
                                      April 1983
 Company —
 Location	
 Test Number.
 Date 	
 Type Facility —
 Control Device
                                         Hours of Observation
                                         Observer 	
                                         Observer Certification Date
                                         Observer Affiliation  	
                                         Point of Emissions  	
                                        o
                                         Height of Discharge Point
Clock Time

Observer Location
  Distance to Discharge

  Direction from Discharge


  Height bf Observation Point


Background Description

Weather Conditions
  Wind Direction

  Wind Speed


  Ambient Temperature


Sky Conditions (clear,
  overcast. % clouds, etc.)

Plume Description
  Color

Distance Visible


Other Information
                               Initial
                                                               Final
                                                                                    Summary of Average Opacity
Set
Number










Time
Stan— End










Opacity
Sum










Average










                                                                               O
                                      Readings ranged from.
                      .to.
.% opacity
                                      The source was/was not in compliance with
                                      	at the time evaluation was made.
Figure 9.1    Record of Visual Determination of Opacity
                                                                                                 Page.
                                                                   .of.
condensed water vapor is no longer
visible. The observer shall record the
approximate distance from the
emission outlet to the point in the
plume at which the observations are
made.
2.3.2  Detached steam plume. When
water vapor in the plume condenses
and becomes visible at a distinct
distance from the emission outlet, the
opacity of emissions should be
evaluated at the emission outlet prior
to the condensation of water vapor
and the formation of the steam plume.

2.4  Recording observations. Opacity
observations shall be recorded to the
nearest 5 percent at 15-second
intervals on an observational record
sheet. (See Figure 9-2 for an
example.) A minimum of 24
observations shall be recorded. Each
momentary observation recorded shall
be" deemed to represent the average
opacity of emissions for a 15-second
period.
2.5  Data Reduction. Opacity shall be
determined as an average of 24
consecutive observations recorded'at
15-second intervals. Divide the
observations recorded on the record
sheet into sets of 24 consecutive
observations. A set is composed of
any 24 consecutive observations. Sets
need not be consecutive in time and
in no case shall two sets overlap. For
each set of 24 observations,  calculate
the average by summing the opacity
of the 24 observations and dividing
this sum by 24. If an applicable
           O

-------
                              April 1983
                            Section 3.12.8
 Company —
 Location	
 Test Number
 Date 	
Observer 	
Type Facility	
Point of Emissions
Hr.




























































Min.
0
1
2
3
4
5
6
7
a
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
Seconds
0




























































15




























































30




























































45




























































Steam flume
(check if applicable)
Attached























'




































Detached





























































Comments




























































Figure 9.2    Observation Record
                           (FR Doc. 74-26150 Filed 11-11-74; 8:45 am}

                                                  Page	of	

-------
                        Section 3.12.8
                                    April 1983
standard specifies an averaging time
requiring more than 24 observations,
calculate the average for all
observations made during the
specified time period. Record the
average opacity on a record sheet.
(See Figure 9-1  for an example.)

3.   Qualifications and testing.

3.1  Certification requirements. To
receive certification as a qualified
observer, a candidate must be tested
and demonstrate the ability to assign
opacity readings in 5 percent
increments to 25 different black
plumes and 25 different white
plumes, with an error not to exceed
15 percent opacity on any one reading
and an average  error not to exceed 7.5
percent opacity  in each category.
Candidates shall be tested according to
the procedures described in paragraph
3.2. Smoke generators used pursuant
to paragraph 3.2 shall be equipped
with a smoke meter which meets the
requirements of paragraph 3.3.
  The certification shall be valid for a
period of 6 months, at which time the
qualification procedure must be
repeated by any observer in order to
retain certification.

3.2  Certification  procedure.
  The certification test consists of
showing the candidate a complete run
of 50 plumes—25 black plumes and
25 white plumes—generated by a
smoke generator. Plumes within each
set of 25 black and 25 white runs
shall be presented in random order.
The candidate assigns an opacity
value to each plume and records  his
observation on a suitable form. At the
completion of each run of 50
readings, the score of the candidate is
determined. If a candidate fails to
qualify, the complete run of 50
readings must be repeated in any
retest. The smoke test may be
administered as part of a smoke
school or training program, and may
be preceded by  training or
familiarization runs of the smoke
generator during which candidates
are shown black and white plumes of
known opacity.


3.3   Smoke generator
specifications.
  Any smoke generator used for the
purposes of paragraph 3.2 shall be
equipped with a smoke meter
installed to measure opacity across
the diameter of  the smoke generator
stack. The smoke meter output shall
display instack opacity based upon a
path  length equal to the stack exit
diameter, on a full 0 to 100 percent
chart recorder scale. The smoke meter
optical design and performance shall
meet the specifications shown in
Table 9-1. The smoke meter shall be
calibrated as prescribed in paragraph
3.3.1 prior to the conduct of each
smoke reading test. At the
completion of each test, the zero and
span drift shall be checked and if the
drift exceeds ±1  percent opacity, the
conditions shall be corrected prior to
conducting any subsequent test runs.
The smoke meter shall  be
demonstrated, at the time of
installation, to meet the specifications
listed in Table 9-1. This demonstration
shall be repeated following any
subsequent repair or replacement of
the photocell or associated electronic
circuitry including the chart recorder
or output meter, or every 6 months,
whichever occurs first.

Table 9-1.    Smoke Meter Design and
             Performance Specifica-
             tions
Parameter:	   Specification
a. Light source    Incandescent  lamp
                  operated at
                  nominal rated
                  voltage.
b. Spectral        Photopic (daylight
response of       spectral response of
photocell.         the human eye—
                  reference 4.3).
c. Angle of view  15° maximum total
                  angle.
d. Angle of projec-15° maximum total
tion              angle.
e. Calibration error ±3% opacity, maxi-
                  mum
f. Zero and span  ±1% opacity, 30
drift.             minutes.
g. Response time  <5 seconds.	

3.3.1  Calibration. The smoke meter
is calibrated after allowing a minimum
of 30 minutes warmup by alternately
producing simulated opacity of 0
percent and 100  percent. When stable
response at 0 percent or 100 percent
is noted, the smoke meter is adjusted
to produce an output of 0 percent or
100 percent, as appropriate. This
calibration shall be repeated until
stable 0 percent and 100 percent
readings are produced without
adjustment. Simulated 0 percent and
100 percent opacity values may be
produced by alternately switching the
power to the light source on and off
while the smoke generator is not
producing smoke.

3.3.2 Smoke meter evaluation. The
smoke meter design and performance
are to be evaluated as follows:
3.3.2.1   Light source. Verify from1"
manufacturer's data and from voltage
measurements made at the lamp, as
installed, that the lamp is operated
within ±5 percent of the nominal
rated voltage.

3.3.2.2  Spectral response of
photocell. Verify from manufacturer's
data that the photocell has a photopic
response; i.e., the spectral sensitivity
of the cell shall closely approximate
the standard spectral-luminosity curve
for photopic vision which is
referenced in (b) of Table 9-1.

3.3.2.3  Angle of view. Check
construction geometry to ensure that
the total angle of view of the smoke
plume, as seen by the photocell, does
not exceed 15°. The total angle of
view may be calculated from: & = 2
tan"1 d/2L, where 6 = total angle of
view; d = the sum of the photocell
diameter + the diameter of the limiting
aperture; and L = the distance from
the photocell to the limiting aperture.
The  limiting aperture is the point in
the path between the photocell and
the smoke plume where the angle of
view is most restricted. In smoke
generator smoke meters this is
normally an orifice plate.

3.3.2.4  Angle of projection. Check
construction geometry to ensure that
the total angle of projection of the
lamp on the smoke plume does not
exceed 15°. The total angle of
projection may be calculated from: 6 =
2 tan"1 d/2L, where 6 = total angle of
projection; d = the sum of the length
of the lamp filament + the diameter of
the limiting aperture; and L = the
distance from the lamp to the limiting
aperture.

3.3.2.5  Calibration error. Using
neutral-density filters of known
opacity, check the error between the
actual response and the theoretical
linear response of the smoke meter.
This  check is accomplished by first
calibrating the smoke meter according
to 3.3.1 and then inserting a series of
three neutral-density filters of
nominal opacity of 20, 50, and 75
percent in the smoke meter
pathlength. Filters calibrated within
±2 percent shall be used. Care should
be taken when inserting the filters to
prevent stray light from affecting the
meter. Make a total of five
nonconsecutive readings for each
filter. The maximum error on any one
reading shall be 3 percent opacity.

3.3.2.6  Zero and span drift.
Determine the zero and span drift by
calibrating and operating the smoke
o
o
o

-------
                            April 1983
                                                                          Section 3.12.8
generator in a normal manner over a
1-hour period. The drift is measured
by checking the zero and span at the
end of this period.

3.3.2.7   Response time. Determine
the response time by producing the
series of five simulated 0 percent and
100 percent opacity values and
observing the time required to reach
stable response. Opacity values of 0
percent and 100 percent may be
simulated by alternately switching the
power to the light source off and on
while the smoke generator is not
operating.

4.   References.

4.1  Air Pollution Control District
Rules and Regulations,  Los Angeles
County Air Pollution Control District,
Regulation IV,  Prohibitions, Rule 50.

4.2  Weisburd, Melvin L.  Field
Operations and Enforcement Manual
for Air, U.S. Environmental-Protection
Agency, Research Triangle Park, N.C.,
APTD-1100, August  1972, pp. 4.1-
4.36.

4.3  Condon,  E.U., and Odishaw, H.,
Handbook of Physics, McGraw-Hill
Co., N.Y., N.Y., 1958, Table 3.1, p.  6-
52.

-------
o
o
o

-------
                          April 1983
                                  Section 3.12.9
                              9.0   References and  Bibliography
 1. Technical Assistance Document:
    Quality Assurance Guideline for
    Visible Emission Training
    Programs, EPA-600/S4-83-011:
 2. Federal Register, Volume 39,
    No. 219, November 12, 1974.
    Method 9 - Visual
    Determination of the Opacity of
    Emissions from Stationary
    Sources (Appendix A).
 3. Conner, W.D. Measurement of
    Opacity by Transmissometer and
    Smoke Readers. EPA
    Memorandum Report. 1974.
 4. Conner, W.D., and J.R.
    Hodkinson. Optical Properties
    and Visual Effects of Smoke
    Plumes. U.S. Environmental
    Protection Agency. Office of Air
    Programs, Edison  Electric
    Institute, and Public Health
    Service. 1967. AP-30.
 5. Coons, J.D., et al. Development,
    Calibration, and use of a Plume
    Evaluation Training Unit. JAPCA
    15: 199-203, May 1965.
 6. Crider, W.L., and J.A. Tash.
    Status Report: Study of Vision
    Obscuration by Nonblack
    Plumes. JAPCA 14:161-165,
    May 1964.
 7. U.S. Environmental Protection
    Agency. Evaluation of EPA
    Smoke School Results. Emission
    Standards and Engineering
    Division, Office of Air Quality
    Planning and Standards. October
    9,1974.
 8. Evaluation and Collaborative
    Study of Method for  Visual
    Determination of Opacity of
    Emissions from Stationary
    Sources. EPA-650/4-75-009.
 9. Malmberg, K.B. EPA Visible
    Emission Inspection  Procedures.
    U.S. Environmental Protection
    Agency, Washington, D.C.
    August 1975.
10. Osborne, M.C., and M.R.
    Midgett. Survey of
    Transmissometer Used in
    Conducting Visible Emissions
    Training Courses. Environmental
    Monitoring and Support
    Laboratory, U.S. Environmental
    Protection Agency. March 1978.
11. Ringelmann, M. Method of
    Estimating Smoke Produced by
    Industrial  Installations. Rev.
    Technique, 268, June 1898.
12.  Weir, A., Jr., D.G. Jones, and
    L.T. Paypay. Measurement of
    Particle Size and Other Factors
    Influencing Plume Opacity.
    Paper presented at the
    International Conference on
    Environmental Sensing and
    Assessment, Las Vegas, Nevada,
    September 14-19, 1975.
13.  U.S. Environmental Protection
    Agency. APTI Course 439
    Visible Emissions Evaluation.
    Student Manual. EPA-450/3-
    78-106, 1978.
14.  U.S. Environmental Protection
    Agency. APTI Course 439
    Visible Emissions Evaluation.
    Instructor Manual. EPA-450/3-
    78-105, 1978.
15.  U.S. Environmental Protection
    Agency. Guidelines for
    Evaluation of Visible Emissions.
    EPA-340/1-75-007. 1975.
16.  U.S. Environmental Protection
 •  Agency. Screening Procedures
    for Ambient Air Quality Data.
    EPA-450/2-78-037, July 1978.
17.  Validation of Air Monitoring
    Data. EPA-600/4-80-030, June
    1980.

-------
o
o
o

-------
                             April 1983                 1                 Section 3.12.10
                                         10.0   Data  Forms
  Blank data forms are provided on
the following pages for the
convenience of the QA Handbook
user. No documentation is given on
these forms because it would detract
from their usefulness. Also, the titles
are placed at the top of the figures, as
is customary for a data form. These
forms are not required format, but are
intended as guides for the
development of an organizations' own
program. To relate the form to the
text, a form number is also indicated
in the lower right-hand corner (e.g..
Form M9-1.1, which implies that the
form is Figure  1.1. in Section 3.12.1
of the Method  9 Handbook). Any
future revisions of this form can be
documented by adding A, B, C (e.g.,
1.1 A, 1.1B). The data forms included
in this section  are listed below.

Form             Title

 1.2 Sample Certification Test Form
 2.1 Procurement Log
 4.1 Visible Emission Observer's
     Plant Entry  Checklist
 4.1 Visible Emission Observer's
     Plant Entry  Checklist (Reverse
     Side)
 4.2 Visible Emission Observation
     Form
 4.2 Visible Emission Observation
     Form (Reverse Side)
 5.1 Visible Emission Summary Data
     Sheet
 6.2 Visible Emission Summary Data
     Sheet (same as Figure 5.1)
 7.1 Method 9 Checklist for Auditors

-------
                      Section 3.12.10
                                                            April 1983
                                         Sample Certification Test Form
Affiliation
                                    Name
Course location
Date.
Distance and direction to stack
 Reading
 number
    J
    2
    3
    4
    5

    6
    7
    8
    9
   10

   11
   12
   13
   14
   15

   16
   17
   18
   19
   20

   21
   22
   23
   24
   25
0  5
0  5
0  5
0  5
0  5

0  5
0  5
0  5
0  5
0  5

0  5
0  5
0  5
0  5
0  5

0  5
0  5
0  5
0  5
0  5
0  5
0  5
0  5
0  5
    10   15   20
    10   15   20
            20
            20
10  15
10  15
    10   15   20

    10   15   20
    10   15   20
    10   IS   20
    10   15   20
    10   15   20

    10   15   20
    10   15   20
    10   15   20
    10   15   20
    10   15   20
   10   15
   10   15
        20
        20
10  15  20
10  15  20
0  5   10   15  20
   10   15   20
            20
            20
10  15
10  15
   W   15
   10   15
        20
        20
                          Sky.
         25  30   35
         25  30   35
         25  30   35
         25  30   35
         25  30   35

         25  30   35
         25  30   35
         25  30   35
         25  30   35
         25  30   35

         25  30   35
         25  30   35
         25  30   35
         25  30   35
         25  30   35
         25  30
         25  30
         35
         35
25   30  35
25   30  35
25   30  35

25   30  35
25   30  35
25   30  35
25   30  35
25   30  35
                                                     Sunglasses
 40  45
 40  45
 40  45
 40  45
 40  45

 40  45
 40  45
 40  45
 40  45
 40  45

 40  45
 40  45
 40  45
 40  45
 40  45

 40  45
 40  45
 40  45
 40  45
 40  45

'40  45
 40  45
 40  45
 40  45
 40  45
 50  55
 50  55
 50  55
 50  55
 50  55

 50  55
 50  55
 50  55
 50  55
 50  55

 50  55
 50  55
 50  55
 50  55
 50  55

 50  55
 50  55
 50  55
 50  55
 50  55

 50  55
 50  55
 50  55
 50  55
 50  55
                                                                       Run Number
                                                                       Wind
                               60  65  70
                               60  65  70
                                       70
                                       70
                               60  65  70
60  65
60  65
                                           60   65  70
                                           60   65  70
                                           60   65  70
                                           60   65  70
                                           60   65  70
                                            60  65
                                            60  65
                                            60  65
                                            60  65
                                       70
                                       70
                                       70
                                       70
                               60  65  70
60  65   70
60  65   70
60  65   70
60  65   70
60  65   70

60  65   70
60  65   70
60  65   70
60  65   70
60  65   70
75  80
75  80
75  SO
75  80
85  90
85  90
85  90
85  90
                                                         75   80  85  90
75  80
75  80
75  80
75  80
75  80

75  80
75  80
75  80
75  80
75  80

75  80
75  80
75  80
75  80
75  SO

75  80
75  80
75  80
75  80
75  80
85  90
85  90
85  90
85  90
85  90

85  90
85  90
85  90
85  90
85  90

85  90
85  90
85  90
85  90
85  90

85  90
85  90
85  90
85  90
85  90
95
95
95
95
95

95
95
95
95
95
95
95
95
95
95

95
95
95
95
95
100
100
WO
1OO
100

100
100
100
100
100
                              95   1OO
                              95   100
                              95   100
                              95   100
                              95   100
100
100
100
100
100

100
100
100
JOO
100
                                                                                                 o
                                                                                            Error
                                                                                          Deviation .
                                                                                      O
 Reading
 number
    1
    2
    3
    4
    5

    6
    7
    8
    9
   10

   11
   12
   13
   14
   15

   16
   17
   18
   19
   20

   21
   22
   23
   24
   25
0  5
0  5
0  5
0  5
0  5

0  5
0  5
0  5
0  5
0  5

0  5
0  5
0  5
0
0
                                                                                            Error
5
5
0  5
0  5
0  5
0  5
0  5
0  5
0  5
0
0
5
5
0  5
10
10
10
10
10

10
10
10
10
10

10
10
10
10
10

10
10
10
10
10

10
10
10
10
10
        15   20  25
        15   20  25
        15   20  25
        15   20
        15   20
         25
         25
15  20   25
15  20   25
15  20   25
15  20   25
15  20   25

15  20   25
15  20   25
15  20   25
15  20   25
15  20   25

15  20   25
15  20   25
15  20   25
15  20   25
15  20   25

15  20   25
15  20   25
15  20   25
15  20   25
     30  35
     30  35
     30  35
     30  35
     30  35
     30  35
     30  35
     30  35
     30  35

     30  35
     30  35
     30  35
     30  35
 40  45
 40  45
 40  45
 40  45
     30  35  40   45
 40  45
 40  45
 40  45
 40  45
 40  45

 40  45
 40  45
 40  45
 40  45
                        30  35   40  45
                     30  35
                     30  35
                     30  35
                     30  35
             40   45
             40   45
             40   45
             40   45
                        30   35  40  45
     30  35
     30  35
     30  35
     30  35
 40  45
 40  45
 40  45
 40  45
        15   20  25   30  35   40  45
 50  55
 50  55
 50  55
 50  55
 50  55

 50  55
 50  55
 50  55
 50  55
 50  55

 50  55
 50  55
.50  55
 50  55
 50  55

 50  55
 50  55
 50  55
 50  55
 50  55

 50  55
 50  55
 50  55
 50  55
 50  55
60  65   70
60  65   70
60  65   70
60  65   70
60  65   70

60  65   70
60  65   70
60  65   70
60  65   70
60  65   70

60  65   70
60  65   70
60  65   70
6O  65   70
60  65   70

60  65   70
6O  65   70
60  65   70
60  65   70
60  65   70

60  65   70
60  65   70
60  65   70
60  65   70
60  65   70
75  SO
75  80
75  80
75  80
75  80

75  80
75  80
75  80
75  80
75  80

75  80
75  80
75  80
75  80
75  80

75  80
75  80
75  80
75  80
75  80

75  80
75  80
75  SO
75  80
75  80
85  90   95
85  90   95
85  90   95
85  90   95
85  90   95

85  90   95
85  90   95
85  90   95
85  90   95
85  90   95

85  90   95
85  90   95
85  90   95
85  90   95
85  90   95

85  90   95
85  90   95
85  90   95
85  90   95
85  90   95

85  90   95
85  90   95
85  90   95
85  90   95
85  90   95
     100
     10O
     100
     too
     100

     100
     100
     100
     100
     100

     100
     too
     100
     100
     100

     100
     100
     100
     100
     100

     100
     100
     JOO
     100
     JOO
                                                                                         Deviation .
           O
                                                                             Quality Assurance Handbook M9-1.2

-------
                           April 1983
                                                     Section 3.12.10
                                               Procurement Log
Item description
Quantity
Purchase
  order
 number
Vendor
                                                             Date
Ordered
Received
Cost
Disposition
Comr-.ents
                                                                                Quality Assurance Handbook U9-2.1

-------
                      Section 3.12.10
                   April 1983
                                  Visible Emission Observer's Plant Entry Checklist
                                                                                                                   o
Source name and address
Observer
                                                      Agency
                                                       Date of VE observation
Previous company contact (if applicable)
Title
Purpose of visit
Emission points at which VE observations to be conducted
                                                                                                                 O
Authority for entry (see reverse side}
Plant safety requirements

D Hardhat
O Safety glasses
D Side shields Ion glasses)
D Goggles
D Hearing protection
  Specify	•- ..
  D Coveralls
  D Dust mask suggested
  D Respirators)
    Specify	
D Safety shoes (steel-toed)
D Insulated shoes
D Gloves
 D Other
 D Specify
Company official contacted (on this visit)
Title
                                                                                                                 O
                                                                                  Quality Assurance Handbook M9-4.1
                                                                                      /

-------
                             April 1983                  5                  Section 3.12.10
                                 Visible Emission Observer's Plant Checklist (Continued)

Authority for Plant Entry: Clean Air Act, Section 114

(a)(2)  the Administrator or his authorized representative upon presentation of his credentials -

        (Aj shall have a right of entry to. upon or through any premises of such person or in which any records required to be
           maintained under paragraph (1) of this section are located,  and

        (B) may at reasonable times have access to. and copy of any records, inspect any monitoring equipment or methods
           required under paragraph (JJ. and sample any emissions which such person  is required to sample under
           paragraph (1).

(b) (JJ   Each State may develop and submit to the Administrator a procedure for carrying out this section in such State. If the
Administrator finds the State procedure is adequate, he may delegate to such State any authority he has to carry out this
section.

   (2)  Nothing in this subsection shall prohibit the Administrator from carrying out this section in a State.
(c)Any records, reports or information obtained under subsection fa) shall be available to the public except that upon a showing
satisfactory to the Administrator by any person that records, reports, or information, or particular part thereof, (other than
emission data) to  which the Administrator has access under this section if made public would divulge methods or processes
entitled to protection as trade secrets of such person, the Administrator shall consider such record, report, or information or
particular portion thereof confidential in accordance with  the  purposes of Section 1905 of Title  J8 of the United States
concerned with carrying out this Act  or when relevant in any proceeding under this Act."


Confidential Information: Clean Air Act, Section 114 (see above) 41 Federal Register 36902, September 1, 1976

  If you believe that any of the information required to be submitted pursuant to this request is entitled to be treated as
confidential, you may assert a claim of business confidentiality,  covering all or any part of the information, by placing on (or
attaching to) the information a cover sheet, stamped or typed legend, or other suitable notice, employing language such as
"trade secret," "proprietary," or  "company confidential." Allegedly confidential portions of otherwise nonconfidential
information should be clearly identified.  If you desire confidential treatment only until the occurrence  of a certain event: the
notice should so state. Information so covered-by a claim will be disclosedby EPA only to theextent, andthrough the procedures.
set forth at 40 CFR.  Part 2, Subpart B (41 Federal Register 369O2, September 1,  1976.)

  If no confidentiality claim accompanies this information when it is received by EPA. it may be made available to the public by
EPA  without further notice to you.


                                                                                  Quality Assurance Handbook M9-4.1

-------
Section 3.12.10
April 1983
                   Visible Emission Observation Form
SOURCE NAME
ADDRESS

CITY
PHONE
STATE
ZIP


SOURCE ID NUMBER
PROCESS EQUIPMENT
CONTROL EQUIPMENT
OPERATING MODE
OPERATING MODE


DESCRIBE EMISSION POINT
START STOP-
HEIGHT ABOVE GROUND LEVEL
START STOP
DISTANCE FROM OBSERVER
START STOP
HEIGHT RELATIVE TO OBSERVER
START STOP
DIRECTION FROM
START S
OBSERVER
TOP
DESCRIBE EMISSIONS
START STOP
EMISSION COLOR
START STOP
WA TER DROPLETS PRESENT:
NOO YESD
PLUME TYPE: CONTINUOUS D
FUGITIVE D INTERMITTENT D
IF WA TER DROPLET PLUME:
ATTACHED D tfETACHEDO
POINT IN THE PLUME A T WHICH OPACITY WAS DETERMINED
START STOP
DESCRIBE BACKGROUND
START STOP
BACKGROUND COLOR
START STOP
WIND SPEED
START STOP
AMBIENT TEMP.
START STOP
Source Layout Sketch
X
. Sun-fy Wind^.
Plume and — ^^,
Stack -^-^T"^
_^^^ ^140
SKY CONDITIONS
START STOP
WIND DIRECTION
START S
WET BULB TEMP.
Draw North Art
C
Emission Point
Observers Position
°'^^^
TOP
RH, percent
ow
)
Sun Location Line
COMMENTS

1 HA VE RECEIVED A COPY OF THESE OPA CITY OBSERVA TIONS
SIGNATURE
TITLE
DATE
OBSERVATION DATE
\SfC
/M//v\
7
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
0






























15












30















































START TIME
45






























A VERA GE OPA CITY FOR
HIGHEST PERIOD
\SfC
MIN\
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
0






























STOP TIME
15






























30






























45






























NUMBER OF READINGS ABOVE
% WERE
RANGE OF OPACITY READINGS
MINIMUM MAXIMUM
OBSERVER'S NAME (PRINT)
OBSERVER'S SIGNA TURE
DATE
ORGANIZATION
CERTIFIED BY
VERIFIED BY
DATE
DATE
                                                                                              o
                                                                                              o
                                                                                              o
                                                            Quality Assurance Handbook M9-4.2

-------
                                April 1983
                Section 3.12.10
                                             Visible Emission Observation Form

 This form is designed to be used in conjunction with EPA Method 9. "Visual Determination of the Opacity of Emissions from Stationary
 Sources." Any deviations, unusual conditions, circumstances, difficulties, etc.. not dealt with elsewhere on the form should be fully noted
 in the section provided for comments. Following are brief descriptions of the type of information that needs to be entered on the form; for a
 more detailed discussion of each part of the form, refer to the "User's Guide to the Visible Emission Observation Form."
 'Source Name - full company name, parent company or division
information, if necessary.
"Sky Conditions - indicate cloud cover by percentage or by
description (clear, scattered, broken, overcast, andcolorofclouds/.
"Address - street (not mailing) address or physical location
of facility where VE observation is being made.

Phone • self-explanatory.


Source ID Number - number from NEDS, CDS, agency fife. etc.

"Process Equipment, Operating Mode • brief description of process
equipment (include ID no.) and operating rate, % capacity utilization,
and/or mode (e.g., charging, tapping).

"Control Equipment, Operating Mode - specify control device type(s)
and % utilization, control efficiency.

"Describe Emission Point- stack or emission point location, geometry,
diameter, color; for identification.purposes.
"Height Above Ground Level - stack or emission point height, from
files or engineering drawings.
"Height Relative to Observer - indicate vertical position of observation
point relative to stack top.


"Distance From Observer - distance to stack ±10%; to determine, use
rangefinder or map.

"Direction From Observer - direction to stack; use compass or map;
be accurate to eight points of compass.

"Describe Emissions - include plume behavior and other physical
characteristics (e.g., looping, lacy, condensing, fumigating, secondary
particle formation, distance plume visible, etc.).

"Emission Color - gray, brown, white, red, black, etc.
Plume Type:
  Continuous - opacity cycle >6 minutes
  Fugitive - no specifically designed outlet
  Intermittent - opacity cycle <6 minutes

"Water Droplets Present • determine by observation or use wet sling
psychrometer; water droplet plumes are very white, opaque, and
billowy in appearance, and usually dissipate rapidly.

"'If Water Droplet Plume:
  Attached • forms prior to exiting stack
  Detached - forms after exiting stack

"Point in the Plume at Which Opacity was Determined - describe
physical location in plume where readings were made (e.g., 4 in. above
stack exit or 10 ft after dissipation of water plume).

"Describe Background - object plume is read against, include
atmospheric conditions (e.g., hazy).

"Background Color - blue, white, new leaf green, etc.
 •Required by Reference Method 9; other items
  suggested.
"Required by Method 9 only when particular
  factor could affect the reading.
"Windspeed - use Beaufort wind scale or hand-held anemometer:
be accurate to ±5 mph.

"Wind Direction - direction wind is from: use compass; be
accurate to eight points.

"Ambient Temperature - in °F or °C.

""Wet BuK> Temperature - the wet bulb temperature from the
sling psychrometer.
""Relative Humidity - use sling psychrometer; use local U.S.
Weather Bureau only if nearby.

"Source Layout Sketch - include wind direction, associated
stacks, roads, and other landmarks to fully identify location of
emission point and observer position.

Draw North Arrow - point line of sight in direction of emission
point, place compass beside circle, and draw in arrow parallel
to compass needle.

Sun Location Line - point line of sight in direction of emission
point, place pen upright on sun location line, and mark location
of sun when pen's shadow crosses the observers position.

""Comments - factual implications, deviations, altercations.
and/or problems not addressed elsewhere.

Acknowledgment - signature, title, and date of company official
acknowledging receipt of a copy of VE observation form.

"Observation Date - date observations conducted.
"Start Time. Stop Time - beginning and end times of observation
period (e.g..  1635 or 4:35 p.m.).

"Data Set - percent opacity to nearest 5%: enter from left to right
starting in left column.
"Average Opacity for Highest Period - average of highest 24
consecutive opacity readings.


Number of Readings Above (Frequency Count) - count of total
number of readings above a designated opacity.


"Range of Opacity Readings:
  Minimum - lowest reading
  Maximum - highest reading

"Observer's Name - print in full.
Observer's Signature, Date - sign and date after performing final
calculations.

"Organization - observer's employer.

"Certifies Ojrtc - name of "smoke school" certifying observer and
date of most recent certification.

Verifier, Date - signature of person responsible for verifying
observer's calculations and date of verification.
                         Quality Assurance Handbook M.9-4.2

-------
                          Section 3.12.10
                                                                              April 1983
                                          Visible Emission Summary Data Sheet
Company .

Start time
                                       .Date
                                                                              . Location
                           . Emission point
                                                                                          o
Stan
no.
t
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
Total
opacity




































Average
opacity




































Start
no.
37
38
39
40
41
42
43
44
45
46
47
48
49
SO
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
Total
opacity




































Average
opacity




































Start
no.
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
S8
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
Total
opacity




































Average
opacity




































Start
no.
109
110
111
112
113
114
115
116
117
116
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
Total
opacity




































Average
opacity




































Start
no.
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
Total
opacity




































Average
opacity




































Start
no.
181
182
183
184
185
186
187
188
189
190
191
192
193
194
195
196
197
198
199
200
201
202
203
204
205
206
207
208
209
210
211
212
213
214
215
216
Total
opacity




































Average
opacity




































                                                                                                                         O
                                                                                                                        o
Maximum average 	
Number of nonoverlapping averages
Calculated by	
.	% Start number of six minute average	/ _
 in excess of standard 	Listing start number of these
	Date	Reviewed by	 Date .
averages .
                                                                                      Quality Assurance Handbook M9-5.1
                                                                                                            andM9-6.2

-------
                               April 1983
                    Section 3.12.10
                                              Method 9 Checklist for Auditors
Name of individual/si audited
Affiliation  	
Auditor name .
Date of audit _
.Affiliation
   .Auditor signature
Yes




















No




















Comment









•










Operation
1. Equipment satisfactory
2. Data forms completed
3. Post-notification (courtesy obligation) performed
4. Correct identification of point of emissions
5. Plume associated with process generation point
6- Credentials okay
7. Observer acted in professional and courteous manner
8. Proper observer position
9- Opacity readings complete
10. Ancillary measurements available
1 1. Camera used to validate siontings/source identification
12. Facility personnel given a copy of raw data
13. Mutiple sources/plumes/outlets
14. Lighting conditions satisfactory
15. Background conditions (raining, etc.) satisfactory
16. Slant angle recorded
1 7. Fugitive emissions
18. Time of day recorded
19. Recertified within last 6 months
General comments:
                                                                                        Quality Assurance Handbook M9-7.1

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o
o
o

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                                                Section No. 3.13
                                                Date July 1, 1986
                                                Page 1
                           Section 3.13
       METHODS 6A AND 6B--DETERMINATIONS OF SULFUR DIOXIDE,
           MOISTURE, AND CARBON DIOXIDE EMISSIONS FROM
                  FOSSIL FUEL COMBUSTION SOURCES
                             OUTLINE
     Section

SUMMARY
METHOD HIGHLIGHTS
METHOD DESCRIPTION
Documentation
    3.13
    3:i3
 Number
of Pages
   1
  10
     1.   PROCUREMENT OF APPARATUS
          AND SUPPLIES
     2.   CALIBRATION OF APPARATUS
     3.   PRESAMPLING OPERATIONS
     4.   ON-SITE MEASUREMENTS
     5.   POSTSAMPLING OPERATIONS
     6.   CALCULATIONS
     7.   MAINTENANCE
     8.   AUDITING PROCEDURE
     9.   RECOMMENDED STANDARDS FOR
          ESTABLISHING TRACEABILITY
    10.   REFERENCE METHODS
    11.   REFERENCES
    12.   DATA FORMS
    3.13.1
  18
3.13.2
3.13.3
3.13.4
3.13.5
3.13.6
3.13.7
3.13.8
3.13.9
3.13.10
3.13.11
3.13.12
14
6
25
15
9
3
11
1
5
2
18

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                                                Section No. 3.13
                                                Date July 1, 1986
                                                Page 2
                             SUMMARY
     For  Method  6A a gas sample is extracted from the stack  in
the same manner as for Method  6  except that C0« is collected in
the sampling train in addition to the S02.  For Method  6B  a gas
sample is extracted from the sampling  point  in the stack inter-
mittently  over a 24-hour or other specified time period.   Samp-
ling  may  also  be conducted continuously for Method 6B  if  the
apparatus and procedures are appropriately modified.  The S02 and
CO, are separated and collected  in  the  sampling train. The S02
fraction is measured by the barium-thorin titration  method,  ana
C0« and moisture are determined gravimetrically.

     This method applies to the determination  of  sulfur dioxide
(S02)  emissions from combustion  sources  in  terms  of  concen-
tration (mg/m )  and  emission  rate (ng/J),  and for the determi-
nation of  carbon  dioxide (C0?) concentration (percent).  Method
6A  gives  results on an hourly basis and Method 6B gives results
on a daily (24 hour) basis.

     The minimum detectable  limit,  upper  limit, and the inter-
ferences for S02 measurements  are .the  same  as  for  Method 6.
EPA-sponsored collaborative studies  were undertaken to determine
the magnitude of repeatability  and reproducibility achievable by
qualified  testers following the procedures in this method.   The
results of the studies evolved from 145 field tests  using 9 test
teams  including comparisons with Methods 3 and 6.  For  measure-
ments of emission rates from wet, flue gas desulfurization  units
in (ng/J), the repeatability (within-laboratory precision) is 8.0
percent and the reproducibility (between-laboratory precision) is
11.1 percent at a measured level of about 400 ppm of S02.

     The  method Descriptions  given  herein  are  based  on the
Reference Methods '   promulgated  December  1,  1982,  and  cor-
rections  and  additions  published  on  March  14, 1984 (Section
3.13.10),  and  on  collaborative  testing.     Blank  forms  for
recording  data  are  provided  in the Method Highlights  and  in
Section 3.13.12 for the convenience of Handbook users.
o
                                                                    o

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                                                Section No. 3.13
                                                Date July 1, 1986
                                                Page 3
                        METHODS HIGHLIGHTS
      Section  3.13  describes  specifications for determination of
 sulfur  dioxide, moisture  and carbon dioxide emissions from fossil
 fuel-fired  combustion  sources.   A gas sample is extracted from
 the  stack in  the same manner as for Method 6 except that moisture
 and   C02  are collected in addition to the S02 in the same train.
 The   Merhod 6A and 6B sampling  trains  are  the  same  with  the
 exception  that  the  Method  6B  train  includes  an  industrial
 timer-switch  for intermittent operation over the 24-hour sampling
 time.   The Method  6B sampling train may be modified to allow for
 low  flow rate continuous  sampling.

      The sulfuric acid and SO3 are removed by  the  filter, probe
 and  midget bubbler with isopropanol with Method 6A.  The sulfuric
 acid is substantially removed by the filter and probe with Method
 6B.   The S02  (and SO,,)  are collected in the two midget impingers
 containing 3  percent and  6 percent hydrogen  peroxide for Methods
 6A and  6B, respectively.  For Method 6B,  the SOg is collected in
 the  impingers also,  and  is  included  in  the SO2 results.  The
 moisture that leaves the  last midget impinger containing hydrogen
 peroxide is then collected  by  Drierite  contained  in the final
 midget bubbler.  The dried gases are then passed through a column
 containing a CO2 absorber (Ascarite, Ascarite  II or 5A molecular
 sieves)  to collect the  CO2-   The  analysis  of  the  collected
 samples  includes  the barium-thorin titration for S02  (same  as
 analysis  for  Method  6)  and  a gravimetric  determination  for
 moisture  and  C02.   Method   6B, "Determination of S02 and  C02
 Daily Average Emissions from Fossil,Fuel Combustion Sources," was
 examined  by collaborative testing.   There was no difference  in
 the   precision  estimates  produced  by  the  intermittent   and
 continuous modes of Method 6B.  Averaged over the  two  modes  of
 operation  and  expressed  as a percent of the average  five  day
values,  the  repeatability estimates are:  S02, 9.8 percent; C02/
 9.9  percent;   and  Emission  Rate  (Ib  per  million  Btu),  8.0
percent.  The reproducibility estimates are:  SO2,  12.9 percent;
 CO2,   13.2  percent;   and  Emission  Rate,   11.1   percent.   The
magnitude  of  both  estimates   of   precision  appeared  to  be
 independent of the material  being  measured.  In addition to the
 above precision data, statistical tests  indicated that there was
no  real  difference  between  the  continuous, intermittent, and
 alternative  reference  methods based on average five-day values.
 The  emission  rate  calculated  by  the  collaborators for  145,
 24-hour runs was  within  2.5 percent of the emission rate of 240
Method 6  and  120 Method 3 analyses determined during the entire
period of collaborative sampling.  Four separate sets of SO2 data
were collected during the collaborative test.  They were, for the
 five-day  average,  Method 6 (387 ppm),  plant monitor  (387  ppm),
collaborators/Method  6B  (393  ppm),   and  the  prime contractor
 analyst/Method  6B (394 ppm).  The experienced analyst ran  eight
samples each  day  for  the  five-day  period  using 5A molecular

-------
                                                Section No. 3.13
                                                Date July 1, 1986
                                                Page 4

sieves in the low flow rate sampling train instead of Ascarite II
(used by collaborators) for C02 analysis.   This test proved that
the  molecular  sieves  absorbed  the CO* quantitatively when the
molecular sieve was properly regenerated prior  to  its use.  The
C02  methods  and  five-day averages were, Method 3 (12 percent),
collaborators/Method 6B (12.02  percent),  and  prime  contractor
analyst/Method 6B (11.8 percent).  Backup  Ascarite II cartridges
after the molecular sieve cartridges  absorbed  no  C02'  further
showing that molecular sieve absorption of C02 was quantitative.

    The collaborative test showed  that  Method  6B  is  a viable
alternative  method  for  continuously  monitoring  S0~  emission
rates.   Quality data capture  was  achieved  by  personnel  with
limited experience.  All of the molecular  sieves  had sufficient
absorptive  capability  for C0? when used as prescribed  in  this
procedure.  The need for regeneration of a new batch of molecular
sieves was noted in a private communication.   For  this  reason,
the  analyst  should recognize the possibility that the molecular
sieves may require regeneration.   The  most  frequent  cause  of
error was failure to pass the post  run leak test required in the
method.  Some other reasons were:  broken glassware  and  spilled
solution, disconnected sample  lines during collection, faulty or
uncalibrated dry gas meters, unusually high C02 weight gain which
the collaborator blamed on weighing errors,  and  low heat in the
flexible connector before the impingers.                            -~

    The blank data forms at the end of the Highlights section may  \	j
be removed from the Handbook and used  in  the pretest, test, and
posttest  operations.   Each form has a subtitle (e.g., Method 6A
or  6B, Figure 5.1) to assist the user in finding a similar  com-
pleted form in the  Method Description (e.g.,  in Section 3.13.5).
On the blank and filled-in  forms,  the  item/parameters that can
cause the most significant errors are indicated with an asterisk.

    The Method Description (Section 3.13.1 to 3.13.9) is based on
the  detailed specifications in  the  Reference  Method  (Section
3.13.10) promulgated  by  EPA oa-December 1, 1982 and corrections
and additions on March 14, 1984. 'J

1.  Procurement of Apparatus and Supplies
    Section3.13.1 gives specifications,  criteria,  and  design
features for the required equipment and materials.   The sampling
apparatus  for  Methods 6A and 6B has the same design features as
that  of Method 6, except for the addition of  a  C02  absorption
column, an industrial timer-switch (for Method  6B), and tempera-
ture control in the sample probe when required.  This section can
be used as a guide for procurement and initial  checks  of equip-
ment and supplies.  The activity matrix (Table 1.1) at the end of
the section is a summary of the details given in the text and can
be used as a quick reference.
                                                                   o
                                                       /^
s

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                                                Section No. 3.13
                                                Date July 1, 1986
                                                Page 5

2.  Pretest Preparations
    Section 3.13.2 describes the required  calibration procedures
for the Method 6A and 6B sampling equipment (same as  Method  6).
A pretest checklist  (Figure 2.5 or a similar form) should be used
to summarize the calibration and other pertinent pretest data.

    Section  3.13.3  describes  the  preparation  of supplies and
equipment needed for the sampling.  The pretest  preparation form
(Figure  3.1  of  Section  3.4.3)  can be used  as  an  equipment
checklist.  Suggestions for  packing  the  equipment and supplies
for shipping are given to help minimize breakage.

    Activity matrices for the calibration  of  equipment  and the
presampling  operations   (Tables  2.1  and  3.1)  summarize  the
activities detailed in the text.

3.  On-Site Measurements
    Section 3.13.4 describes procedures  for  sampling and sample
recovery.  A checklist  (Figure  4.7 or 4.8) is an easy reference
for field personnel to use in all sampling activities.

4.  Posttest Operations
    Section  3.13.5  describes  the postsampling  activities  for
checking  the  equipment  and  the analytical procedures.  A form
(Figure  5.1)  is given for  recording  data  from  the  posttest
equipment  calibration  checks;  a  copy  of  the  form should be
included in the emission test final report.  A control  sample of
known (SC^) concentration should be analyzed before analyzing the
sample  for a quality control check on the analytical procedures.
The detailed analytical procedures can be removed for use  as  an
easy reference in the laboratory. . An activity matrix (Table 5.1)
summarizes the postsampling operations.

    Section  3.13.6  describes  calculations,  nomenclature,  and
significant  digits  for the data reduction.  A programmed calcu-
lator is recommended to reduce calculation errors.

    Section  3.13.7 recommends routine and preventive maintenance
programs.  The programs are not required, but  their  use  should
reduce equipment downtime.

5.  Auditing Procedures
    Section  3.13.8  describes  performance  and  system  audits.
Performance  audits  for  both the analytical phase and the  data
processing  are  described.  A checklist (Figure 8.2) outlines  a
system audit.

    Section  3.13.9 lists the  primary  standards  to  which  the
working standards or calibration standards should be traceable.

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                                                Section No. 3.13
                                                Date July 1, 1986
                                                Page 6

6.  References
    Section 3.13.10  contains  the  promulgated Reference Method;
Section  3.13.11  contains  the  references  used throughout this
text;  and  Section 3.13.12 contains copies of data forms  recom-
mended for Method 6A and 6B.
o
                                                                     o
                                                        v
 o

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                                                Section No. 3.13
                                                Date July 1, 1986
                                                Page 7
                      PRETEST SAMPLING CHECKS
                  (Methods 6A and 6B, Figure 2.5)
Date 	   Calibrated by

Meter Box Number
Rotameter

Pretest calibration factor (Y ) acceptable? 	yes  	no
  (within 10 percent of correct value).

                             *
Dry Gas Meter (If applicable)

Pretest calibration factor (Y) = 	(within 2 percent of
  average factor for each calibration run).


Gas Meter Thermometer (If applicable)

Temperature correction necessary? 	yes 	no
  (within 3 C (5.4 F) of reference values for calibration and
  within 6 C (10.6 F) of reference values for calibration
  check).

If yes, temperature correction 	
Barometer     !

Field barometer reading correct? 	yes 	no
  (within 2.5 mm (0.1 in.) Hg of mercury-in-glass barometer).'


Balance

Was the pretest calibration of balance correct? 	yes 	no
  (within 0.05 g of true value using Class S weights).
 Most significant items/parameters to be checked.
                                                  .  i<:)'-'

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                            Section No. 3.13
                            Date July 1, 1986
                            Page 8
     PRETEST PREPARATIONS
(Methods 6A and 6B, Figure 3.1)
o
Apparatus check
Probe
Type liner
Glass
Stainless
steel
Other
Heated properly
Leak checked on
sampling train
Filter or Filter
Assembly
Glass wool
Other

Glassware
Midget bubbler
Midget impinger
Size
Type

Meter System
With timer 	
Without timer
Leak- free pump*^
Rate meter*
Dry gas meter*
Reagents
Distilled water
H2°?' 30 Percen't
ISopropanol, 100%*
(for Method 6A)
Drierite
Ascari£e
or 5A molecular
sieve*

Other
Barometer
COp absorber
column
Balance
Acceptable
Yes






No






Quantity
required






Ready
Yes






NO






Loaded
and packed
Yes






NO






* Most significant items/parameters to be checked.
                                                O
                                               o
                                    .w

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                                                Section No. 3.13
                                                Date July 1, 1986
                                                Page 9
                       ON-SITE MEASUREMENTS
                     (Method 6A, Figure 4.7)
Sampling
Bubbler and impinger  contents  properly  selected,  measured,  and
placed in proper receptacle?*	
Impinger Contents/Parameters

1st:  15 ml of 80 percent isopropanol* 	
2nd:  15 ml of 3 percent H2O2*	
3rd:  15 ml of 3 percent ^2Q2*	
4th:  approx. 25 g of Drierite*	
150 g of Ascarite in CQ2 absorber?*	
Probe heat at proper level?	
Crushed ice around impingers?	
Pretest leak check at 250 mm (10 in.) Hg? 	
Leakage rate?	
Probe placed at proper sampling point? 	
Flow rate constant at approximately 1.0 L/min?*	
Posttest leak check at 250 mm (10 in.) Hg?*	
Leakage rate? 	
Sample Recovery
Balance calibrated with Class S weights?*	
Impingers cleaned and weighed to +0.1 g at room temp?	
Contents of impingers and rinsings placed in polyethylene
 bottles?	
Fluid level marked?*	
C02 absorber cleaned and weighed to HrO.l g at room temp?
Sample containers sealed and identified?* 	
Samples properly stored and locked? 	
 Most significant items/parameters to be checked.
                                                   (>

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                                                Section No. 3.13
                                                Date July 1, 1986
                                                Page 10
                       ON-SITE MEASUREMENTS
                     (Method 6B, Figure 4.8)
Sampling
Impinger contents properly selected, measured, and placed in
impingers?* 	

Impinger Contents/Parameters
1st:  Empty* 	
2nd:  15 ml of >6 percent H202*	
3rd:  15 ml of >6 percent ^2°2*	
4th:  Approx. 25 g of Drierite*__	__
Approx.  150  g of Ascarite II or 250 g 5A* molecular sieve (contin-
uous flow rate train only) in C02 absorber?*	
Probe heat at proper level?
Crushed ice around impingers?	
Pretest leak check at 250 mm (10 in.) Hg? 	
Leakage rate?	
o
Probe placed at proper sampling point? 	
Flow rate intermittent at approximately 1.0 L/min?
Flow rate constant between 20 to 40 ml/min? 	
Posttest leak check at 250 nun (10 in.) Hg? 	
Leakage rate?	
o
Sample Recovery
Balance calibrated with Class S weights?	
Impingers cleaned and weighed to +0.1 g at room temp?	
Contents of impingers and rinsings placed in polyethylene
  bottles?
Fluid level marked?
C02 absorber cleaned and weighed to +0.1 g at room temp?*_
Sample containers sealed and identified?*	
Samples properly stored and locked? 	
*Most significant items/parameters to be checked.
                                                                    O

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                                                Section No.  3.13
                                                Date July 1,  1986
                                                Page 11
                     POSTTEST SAMPLING CHECKS
                  (Methods 6A and 6B, Figure 5.1)
Meter Box Number
Dry Gas Meter (If applicable)

Pretest calibration factor (Y) = 	
Posttest check Y_ = 	 (+_5 percent of pretest
  factor)*      ^
Recalibration required? 	yes 	no
If yes, recalibration factor (Y) = 	(within 2 percent of
  calibration factor for each calibration run)
Lower calibration factor Y (pretest or posttest) = 	
  for calculations


Rotameter

Pretest calibration factor (Y ) = 	
Posttest check (Y ) = 	(within 10 percent of pretest
  factor)        r
Recalibration recommended?  	yes  	no
If performed, recalibration factor (Y ) = 	
Was rotameter"cleaned?   	yes   	no


Dry Gas Meter Thermometer (If applicable)

Was a pretest meter temperature correction used?  	yes  	no
If yes, temperature correction	
Posttest recalibration required?yesno (recali-
  brate when YT  recalibrated)
              Ll


Barometer

Was pretest field barometer reading correct?   	yes   	no
Posttest recalibration required?   	yes   	no (recali-
  brate when Y_  recalibrated)
              LI


Balance*

Was the balance calibration acceptable?  	 yes 	 no
   (+_ 0.05 g checked against Class S weights)
If no, the balance should be repaired or replaced prior to
  weighing field samples
* Most significant items/parameters to be checked.

                                                         ;)7

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                                                Section No. 3.13
                                                Date July 1, 1986
                                                Page 12
                        POSTTEST OPERATIONS
                  (Methods 6 A and 6B, Figure 5.4)
Reagents
Normality of sulfuric acid standard* 	
Date purchased 	  Date standardized
Normality of barium perchlorate titrant* 	
Date standardized
Normality of control sample*
Date prepared
Volume of burette                  Graduations
Sample Preparation
Has liquid level noticeably changed?* 	
Original volume 	  Corrected volume
Samples diluted to 100 ml?*
Analysis
(Sulfur dioxide)
Volume of aliquot analyzed* 	
Do replicate titrant volumes agree within 1 percent or 0.2 ml?
Number and normality of control samples analyzed 	
Are replicate control samples within 0.2 ml?	
o
Is accuracy of control sample analysis ^5 percent?	
Is the relative error of audit sample(s) within acceptable
  limits?*
(Moisture and carbon dioxide)
Balance calibrated with Class S weights to within 0.05 g?*
Initial weight of each impinger to nearest 0.1 g* 	
Final weight of each impinger to nearest 0.1 g*  	
Initial weight of C02 absorber to nearest 0.1 g* 	
Final weight of C02 absorber to nearest 0.1 g*  	
All data recorded?  	    	   Reviewed by
* Most significant items/parameters to be checked,
O

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 I
"*u     1.0  PROCUREMENT OF APPARATUS AND SUPPLIES
                                                     Section No. 3.13.1
                                                     Date July 1, 1986
                                                     Page 1
           A schematic diagram of an assembled Method  6A  and  6B sam-
      pling  train  with  all  components identified is shown in Figure
      1.1.  An alternative sampling train is shown  in  Section 3.13.4,
      page 11.  This sampling train uses larger impingers  and  may  be
      more suitable for many facilities.  Specifications, criteria, and
      design features are given in this section to aid in the selection
      of equipment and to ensure that the collected  data  are  of good
      quality.  Procedures and, where applicable, limits for acceptance
      checks are given.

           During the procurement of  equipment  and  supplies,  it  is
      suggested  that a procurement log be used to record the  descrip-
      tive  title  of  the  equipment, the  identification  number,  if
      applicable, and the results of Acceptance  checks.  An example of
      a procurement log is shown in Figure  1.2.  A blank form is given
      in Section 3.13.12 for  the  Handbook  user.   If  calibration is
      required as part of the acceptance check, the  data  are recorded
      in  the calibration log book.  For facilities that currently have
      Method 6A or Method 6B  sampling  trains  that are operating in a
      satisfactory  manner,  these  procedural   checks   will  not  be
      necessary.   Table  1.1 at the end of this section summarizes the
      quality assurance activities  for  procurement  and acceptance of
      apparatus and supplies.

      1.1   Sampling

      1.1.1    Sampling  Probe - The sampling probe should be either  a
      borosilicate  (Pyrex) glass or  a  type-316  seamless,  stainless
      steel tube of approximately 6-mm inside diameter (ID), encased in
      a stainless steel sheath and equipped  with a heating system cap-
      able of preventing water condensation  and  with a filter (either
      in-stack or heated out-of-stack) to  remove  particulate  matter,
      including  sulfuric  acid mist.  Typically, an in-stack filter is
      used at  non-scrubber  controlled  power plants and a temperature
      controlled out-of-stack filter  is  used  at  scrubber controlled
      power plants.  Stainless steel sampling probes, type-316, are not
      recommended for use with Method 6B because of potential corrosion
      and  contamination  of sample.  Glass probes or  other  types  of
      stainless steel,   e.g., Hasteloy or Carpenter 20, are recommended
      for  long-term  use.   When  an in-stack filter is utilized,  the
      probe should have an expanded diameter (38-40 mm) for  the  first
      4 cm on the in-stack  end, and this expanded end should be packed
      with glass wool prior to sampling.  The probe's opposite end must
      have a fitting suitable for attaching  it  to the midget bubbler.
      A  probe  of approximately 1.2 m (4 feet) total length is usually
      sufficient for sampling.  However, the probe tip can be no closer
      than 1 m (3.28 feet) from the inner wall of stacks >2 m in diame-
      ter.   When stack gas temperatures  exceed  480 C (900 F), a probe
      fabricated  from  quartz  (Vycon)  should  be  used.   The   main
                                                             o

-------
                                  HEATED PROBE AND
                                  OUT-OF-STACK FILTER
                                       MIDGET IMPINGERS
                                                              THERMOMETER _
                                                              (not required
                            WOOL
.1
jj
IT
1 1
1 1
u
t \

— — — •


A

h
u

1 1
I
u
/ \

-—-*-——
-

B

1
.1
4-f
-IU.
|

U
/
1
	 r
	 -+
I
C |
1
                                                        111
                                                        "II  D
                                                        LLi!
                                       WATER BATH (6A ^ly)
  \             /
  MIDGET BUBBLERS
                       THERMOMETER
Method 6A
A - 15 ml of Isopropanol
B - 15 ml of 3% H^O,
C - 15 ml of 3% H^Oj
D - approx 25 g ot  urierite
E - approx 150 g  of Ascarite
Method 6B
A - empty (glass wool not  used)
B - 15 ml of >6% H9O9
C - 15 ml of >6% H^
D - approx 25 g of Drierite
E - approx 150 g of Ascarite
  1DRY
  GAS
  METER
                                                                    C0?
                                                                 ABSORBER-1
                           NEEDLE
                           VALVE
                                                     \
                                                                               CO- BREAKTHROUGH
                                                                               -  INDICATOR
                                                                               (r e c oinine n de d)
                                                                               PUMP
                                                     SURGE TANK
                                                                        TIMER
                                                                       (6B only)
    O
Figure 1.1.  Sampling train.
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                                                                                                  CO
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                                                                                            O

-------
Item description
^^ bo* (Met, (*)
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Purchase
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-------
                                               Section No. 3.13.1
                                               Date July 1, 1986
                                               Page 4

criterion in selecting a probe material is that it be nonreactive   (   j
with the gas  constituents so it does not introduce bias into the   —
analysis.

     A new probe should be checked for  specifications (i.e.,  the
length and composition ordered).  It should be checked for cracks
and breaks,  and  then  leak checked on a sampling train, as des-
cribed  in  Section 3.13.3.  The probe heating system  should  be
checked as follows:

     1.   Connect the probe to the inlet of the pump.

     2.   Electrically connect and turn on the probe heater for 2
or 3 minutes.   If  functioning  properly, it will become warm to
the touch.

     3.   Start the pump and adjust the needle valve until a flow
rate of about 1.0 L/min is achieved.

     4.    Check  the probe.  It should remain warm to the touch.
The heater  must  be  capable of maintaining the exit air temper-
ature at a minimum of 100 C (212 F) under these  conditions.   If
it  cannot,  the  probe  should  be  rejected.    Any  probe  not
satisfying the acceptance check  should be repaired, if possible,
or returned to the supplier.

1.1.2   Filter - A heated out-of-stack filter to remove  particu-   (   )
late, including sulfuric acid  mist.   The  outlet filter temper-   ^~>^
ature  should  be  monitored   and   controlled   to  maintain  a
temgerature sufficient to prevent condensation or to a maximum of
120 C (248 F).  A plug of approximately 0.6 grams of borosilicate
glass  wool with no heavy metals, practically free from  fluorine
and alumina,  low  alkali  content,  and a fiber diameter between
0.005  and  0.008  mm  is  recommended for the filter media.  The
filter holder may be constructed  as  shown  in  Figure 1.3.  The
filter heater should be checked by connecting it to the probe and
following  the  procedures  described above in Subsection  1.1.1.
Caution;  Do not  pack  filter  media  too  tightly, as this will
result in a high pressure drop across the filter.

1.1.3    Flexible Connector (optional) - A heated  flexible  con-
nector may be used between  the exit of the heated filter and the
inlet of the  first  impinger.   The  heated  flexible  connector
should  be Teflon (other construction  materials may be used) and
heated to prevent condensation.  The  flexible  connector  can be
checked using the same  procedure  as  for  the  probe  with  the
exception that it should be checked without connecting it to  the
probe.
1.1.4    Midget Bubbler/lmpingers - Each sampling train  requires
two midget bubblers(30-ml)  of  medium  coarse glass frit,  with
                                                                    o

-------
                                                   Section No. 3.13.1
                                                   Date July 1, 1986
                                                   Page 5
                          THERMOCOUPLE
                                                      TO TEMPERATURE
                                                      CONTROLLER
                                                               -*_ OUTLET
                       4-in. LONG
                       ij-in. DIA.
                       316 STAINLESS STEEL TUBING
            SWAGELOK
               FILTER HOLDER WITH THERMOCOUPLE TO MONITOR
                           EXIT TEMPERATURE.
         INLET
3/8-in.  SWAGELOK
    FITTING
      OUTLET
h-in. SWAGELOK
  FITTING
                                   4-in. LONG
                                   %-in. DIA.
                                   316 STAINLESS STEEL
               FILTER HOLDER WITHOUT TEMPERATURE MONITOR.
                    Figure 1.3.  Out-of-stack  filters.

-------
                                               Section No.  3.13.1
                                               Date July 1,  1986
                                               Page 6                x~v

glass wool packed in the top of the first to prevent carryover of     ^—'
sulfuric acid mist.  A midget  impinger  may  be used in place of
either  midget  bubbler.   Larger impingers, such as the Mae West
design, may also be used.

     Each  sampling  train requires two midget impingers  (30-ml)
with glass connections between the midget bubblers and the midget
impingers.  (Plastic  or  rubber  tubing is not permitted because
these materials absorb  or  desorb  gaseous  species.)   Silicone
grease may be used to prevent leakage.

     Each bubbler/impinger  is  checked visually for damage, such
as breaks or cracks, and for manufacturing  flaws, such as poorly
shaped connections.

     Other nonspeqified collection absorbers  and  sampling  flow
rates  may be used, subject to the approval of the Administrator,
but collection efficiency must be shown to be at least 99 percent
for each  of  three  test  runs  and  must  be  documented in the
emission  test report.  For efficiency testing, an extra absorber
must be added and  analyzed  separately and must not contain more
than 1 percent of the total SO-.

1.1.5   CO? Absorber  -  A  sealable  stainless  steel or plastic
cylinder or glass bottle with  an  inside diameter between 30 and
90  mm  and a length between 125 and 250 mm and with  appropriate
connections  at  both  ends is required.  The cylinder should  be
checked for flaws or cracks and its ability to  hold the required
150 g of Ascarite or 250 g of 5A molecular sieve.  The ability to
remain leak free can be checked at the same time that the new lot
of Ascarite or 5A molecular sieve is  checked  for acceptability,
as later described in Subsection 1.4.1.

     It is strongly recommended that a  second,  smaller  CO- ab-
sorber containing  Ascarite  be  added  in-line downstream of the
primary CO- absorber as a breakthrough indicator.  Ascarite turns
white  when  CO- is absorbed.  Alternatively, a larger  container
can be used witn the primary and secondary  absorber separated by
glass wool.  The thermometer following the CO-  absorber  is  not
required.

1.1.6   Vacuum Pump  - The vacuum pump should be capable of main-
taining a flow rate of approximately 1 to 2 L/min for pump  inlet
vacuums up to 250 mm (10 in.) Hg with the pump outlet near  stan-
dard  pressure, that is 760 mm (29.92 in.) Hg.  The pump must  be
leak free when running and  pulling  a  vacuum (inlet plugged) of
250  mm  (10  in.)  Hg.  Two types of vacuum pumps  are  commonly
used—either a modified sliding fiber vane  pump  or  a diaphragm
pump.   For  safety reasons, the pump should be equipped  with  a
three-wire electrical cord.
                                                                   o

-------
                                               Section No. 3.13.1
                                               Date July 1, 1986
                                               Page 7

      To  check the pump  for leaks, install  a  vacuum gauge in the
 pump  inlet  line.  Plug  the inlet line, and run the pump until the
 vacuum gauge reads 250  mm (10 in.) Hg of vacuum,  then  clamp the
 pump  outlet  line,  and  turn  off the pump.  The vacuum reading
 should remain stable for 30 seconds.

 1.1.7   Volume Meter -  A volume meter  is  not required or needed
 for many applications.  The tester should check the need prior to
 purchase.   The dry gas  meter must be capable  of  measuring total
 volume with an accuracy of +2 percent, calibrated at the selected
 flow  rate of 1.0 L/min.  and  at  the  gas  temperature  actually
 encountered during sampling, and must be equipped  with a temper-
 ature gauge  (dial   thermometer,   or  equivalent)  capable  of
 measuring   the gas temperature to within 3 C (5.4°F).   A  volume
 meter is   necessary if C0~ and  SO.-  concentrations  are  to  be
 measured.

      A new  dry gas  meter  may be checked for damage visually and
 by performing a calibration according to Section 3.13.2.  Any dry
 gas meter that is damaged, behaves erratically,  or does not give
 readings within 2 percent  of the selected flow rate for each run
 is unsatisfactory.  Also upon receipt,  the meter should be cali-
 brated over a varying flow range to see if there is any effect on
 the calibration.

      Dry gas meters that are equipped  with temperature compensa-
 tion  must be calibrated over the entire range of temperature that
 the meter will encounter under actual field conditions.  The cal-
 ibration  must  contain  at  least  one  data  point at each 10 F
 interval.  All temperatures that are to be used in the field must
 be within 2 percent of the calibrated value.

      The wet test meter used to check the  dry  test meter should
 be  calibrated using the primary displacement technique explained
 in Section 3.13.2.  The wetqtest meter must have a capacity of at
 least 0.003 m /min (0.1  ft /min) with an accuracy of +1 percent;
otherwise at the higher  flow  rates, the water will not be level
 and this will possibly result in incorrect readings.

 1.1.8   Rotameter - A rotameter, or its equivalent, with  a range
of 0  to 2 L/min is used to monitor and control the  sampling flow
rate.    The  rotameter  is checked against the calibrated dry gas
meter  with  which it is to be used or against a wet test  meter.
 The rotameter should be within 5 percent of true value or be able
 to be set to within 5 percent of true value.  The rotameter  flow
 setting of about 1 L/min should be determined.
                                •
     Changes  in  pressure,   density, and viscosity of the sample
gas will affect  the  calibrated  sample  rate.   However,  since
 sampling at a constant rate is the intent, these changes need not
be considered.

-------
                                               Section No.  3.13.1
                                               Date July 1,  1986
                                               Page 8

1.1.9   Needle Valve - A metering valve  with  conveniently sized
fittings is required in the sampling train to  adjust  the  sample
flow rate.  It is recommended that the needle valve be placed  on
the vacuum side of the pump.

1.1.10   Thermometers - A dial thermometer,  or its equivalent,  is
used to measure the temperature of gas leaving the impinger train
to within 1  C (2 F).  Dial type thermometers are easily damaged,
so each new thermometer  must be checked visually for damage such
as a dented or  bent stem.  Each  thermometer should read  within
1  C (2 F)  of  the  true value when checked in an ice water bath
and  at  room  temperature against a mercury-in-glass thermometer
that conforms to ASTM E-l  No.  63C or 63F.   Damaged thermometers
that cannot be calibrated must be rejected.

1.1.11   Metering System  -  For ease of use, the metering  system
(if  required)—which contains the dry gas meter, thermometer(s),
vacuum pump, needle valve,  and  rotameter--can be assembled into
one  unit  (meter box).   After  a  meter  box  has  been  either
constructed  or  purchased, then positive and  negative  pressure
leak checks  should  be  performed.   The  positive pressure leak
check, similar  to  the  procedure described in Method 5 (Section
3.4), is performed as follows:

     1.   Attach  rubber  tubing and inclined manometer, as shown
in Figure 1.4.

     2.   Shut  off  the  needle  valve  and blow into the rubber
tubing until the inclined manometer or magnehelic  gauge  reads a
positive pressure of 12.5 to 17.5 cm (5 to 7 in.) H20.

     3.   Pinch off the tube,  and  observe  the  manometer for 1
minute.  A loss of pressure indicates a leak in the apparatus  in
the meter box.

     After the  meter  box apparatus has passed the positive leak
check,  then  the  negative  leak  check  should be performed  as
follows:

     1.   Attach the vacuum gauge at the inlet, and pull a 250 mm
Hg (10 in.) vacuum.

     2.   Pinch  or clamp the outlet of the flow meter.  This can
be  accomplished  by  closing  the  optional  shutoff  valve,  if
employed.

     3.   Turn off the pump.  Any deflection noted in the  vacuum
reading within 30 seconds indicates a leak.

     4.   Carefully release the vacuum gauge before releasing the
flow meter end.
 o
o
                                                                   o

-------
BLOW INTO TUBING

UNTIL MANOMETER

READS 5 to 7 INCHES

WATER COLUMN
                                             THERMOMETER
     RUBBER

     TUBING
                       T-CONNECTOR
     INCLINED

     MANOMETER
                    NEEDLE VALVE

                   ,	 (CLOSED)
\	 SURGE TANK
                    Figure 1.4.  Meter box  leak check.
                                                                    PUMP
                                                                             *o a w
                                                                             CD o> a>
                                                                             IQ d- O
                                                                             (D (D rf
                                                                                 H-
                                                                             «J CL( O
                                                                               C D
                                                                                 (A)
                                                                               00 CO

-------
                                               Section No. 3.13.1
                                               Date July 1, 1986
                                               Page 10

     If  either  of  these  checks  detects a leak that cannot be
corrected,  the meter box  must  be  repaired,  rejected,  and/or
returned to the manufacturer.

     The dry gas meter must be equipped with a temperature  gauge
(dial thermometer  or  equivalent).   Each thermometer is checked
visually for damage, such as  dented  or bent face or stem.  Each
thermometer should read within 3 C (5.4 F) of the true value when
checked  at  two  different  ambient   temperatures   against   a
mercury-in-glass thermometer that conforms to ASTM E-l No. 63C or
63F.  The two ambient temperatures used to calibrate the thermom-
eter  must  differ  by   a   minimum  of  10 C  (18 F).   Damaged
thermometers that cannot be calibrated are to be rejected.

Note;   The metering  system  may not be required or necessary for
many applications of Method 6A or 6B.   The tester  should  deter-
mine the necessity of a dry gas meter.   Both  Method  6A  and 6B
will determine an  emission  rate  without  the use of a metering
system.  However, if  concentration  data are desired, a metering
system will be necessary.

1.1.12    Barometer  -  A  mercury,  aneroid, or other  barometer
capable  of  measuring  atmospheric  pressure  to within  2.5  mm
(0.1 in.) Hg may be used.  However, in many cases, the barometric
reading  can be obtained from a nearby National  Weather  Service
Station,  in  which case the station value (which is the absolute
barometric pressure) is requested.   The  tester  should be aware
that  the  pressure  is  normally  corrected  to sea level.   The
station value is the uncorrected reading.  An adjustment for dif-
ferences  in elevations of the weather station and sampling point
is applied at a rate of -2.5 mm Hg/30 m (-0.1 in. Hg/100  ft)  of
elevation increase, or vice versa for elevation decrease.

     Accuracy  can  be  ensured  by  checking the field barometer
against a mercury-in-glass barometer or  its  equivalent.  If the
field  barometer  cannot  be  adjusted to agree with the mercury-
in-glass barometer, it is not acceptable.

1.1.13   Vacuum Gauge  - At least one 760-mm (30-in.) Hg gauge is
necessary to leak check the sampling train.  An acceptable vacuum
gauge, when checked in a parallel leakless  system with a mercury
U-tube manometer at 250-mm (10-in.) Hg vacuum, will  agree within
25 mm (1.0 in.) Hg.

1.1.14   Industrial Timer  (For  Method  6B only) - An industrial
timer-switch designed to operate in the "on" position  at least 2
minutes  continuously  and "off"  the  remaining  period  over  a
repeating  cycle.   The  cycle  of operation is designated in the
applicable regulation.  At a minimum,  operation should include at
least 12 equal,  evenly spaced periods of sampling  per  24 hours.
Longer  sampling  durations greatly reduce  the  significance  of
sampler timer error.
 o
o

-------
                                               Section No.  3.13.1
                                               Date July 1, 1986
                                               Page 11
     Initially check the timer as follows:
     1.   Set the  sampling  sequence as it will normally be used
(i.e., 12 equally spaced, 2-minute samples for a 24-hour period).

     2.    Turn  on the sample console (meter  box)  without  the
impinger train.

     3.   Determine the exact volume that  is  metered for one of
the equally spaced sample times.

     4.   Operate the sample console for a 24-hour period.

     5.   The total  sample  volume collected should be within 10
percent of the number of times of the equal spacing.

     If the industrial timer cannot meet these  specifications it
should be repaired or rejected.

1.1.15    Other  Sampling Apparatus - Other  sampling  equipment,
such  as  Mae  West bubblers and  rigid  cylinders  for  moisture
absorption  which  require  sample or reagent volumes other  than
those specified in this procedure for full effectiveness,  may be
used subject to the approval of the Administrator.

1.2   Sample Recovery Apparatus

1.2.1    Wash  Bottles  -  Two 500-ml polyethylene or glass  wash
bottles  are  needed  for  quantitative   recovery  of  collected
samples.

1.2.2    Storage  Bottles  -  One 100-ml polyethylene  bottle  is
required to store each  collected  sample.   An  additional poly-
ethylene bottle is necessary to retain a blank for each absorbing
solution used in testing.  Wash  and  storage  bottles  should be
visually checked for damage.  In  addition,  check  each  storage
bottle seal to prevent sample leakage during transport.

1.3   Analysis Glassware

1.3.1   Pipettes - Several volumetric pipettes (Class A), includ-
ing 5-, 10-,20-, and 25-ml sizes, are required for the analysis.

1.3.2    Volumetric  Flasks  -  Volumetric  flasks  (Class A) are
required in 50-, 100-, and 1000-ml sizes.

1.3.3   Burettes - A 50-ml standard burette (Class A) is required
for all titrations.

1.3.4    Erlenmeyer  Flasks  -  One  250-ml Erlenmeyer  flask  is
required for each sample, blank, standard, and control sample.


-------
o
                                               Section No.  3.13.1
                                               Date July 1,  1986
                                               Page 12

1.3.5    Dropping  Bottle - One 125-ml glass dropping  bottle  is
needed to prepare the thorin indicator.

1.3.6   Graduated Cylinder  -  A 100-ml glass (Class A) graduated
cylinder is needed in the preparation of the thorin indicator and
the sample.

     All  glassware  must  be  checked  for cracks,  breaks,  and
discernible manufacturing flaws.

1.3.7   Balance - A field balance capable of weighing  the midget
impingers and the CO,, absorber  column  with an accuracy of 0.1 g
is  needed.   The  balance  may  be  checked upon initial receipt
against Class S weights.

1.4   Reagents

     Unless otherwise indicated, it is intended that all reagents
conform to the specifications  established  by  the  Committee on
Analytical Reagents of the American Chemical Society (ACS),  where
such  specifications are available; otherwise the best  available
grade is to be used.

1.4.1   Sampling -

     Water - Use deionized distilled  water  to  conform  to ASTM
specification  D 1193-74, Type 3.  At the option of the  analyst,
the KMnO. test  for oxidizable organic matter may be omitted when
high  concentrations  of  organic  matter  are not expected to be
present.

     Isopropanol, 80 Percent (Method  6A)  - Mix 80 ml of isopro-
panol (100 percent)with2"0mlofdeionized distilled water.
Check each lot of isopropanol for peroxide impurities as follows:

     1.    Shake  10  ml  of isopropanol with 10  ml  of  freshly
prepared 10 percent potassium iodide (KI) solution.

     2.   Prepare a blank by similarly treating 10 ml of water.

     3.    After  1 minute, read the absorbance  of  the  alcohol
sample  against  the  H~O blank at 352 nm on a spectrophotometer.
If absorbance exceeds 0.1, reject the alcohol for use.  Peroxides
may  be  removed  from  isopropanol by redistilling or by passing
through  a  column  of  activated  alumina.   After peroxides are
removed, check for peroxide  impurities  using the same method as
above.   However,  reagent  grade  isopropanol  with suitably low
peroxide  levels  may   be   obtained  from  commercial  sources.
Therefore, rejection of contaminated lots may be a more efficient
procedure.
o

-------
                                               Section No. 3.13.1
                                               Date July 1, 1986
                                               Page 13

     Hydrogen Peroxide, 3 Percent (Method 6A) - Dilute 30 percent
hydrogen  peroxide 1:9 (v/v) with water.   Prepare  fresh  daily.
The 30  percent  hydrogen  peroxide should be stored according to
manufacturer's directions.

     Hydrogen Peroxide, 6 Percent (Method 6B) - Dilute 30 percent
hydrogen peroxide 1:3 (v/v) with water.  This  mixture results in
7.5  percent H202; it should be acceptable  for  one  week  in  a
closed  container.  The 30 percent hydrogen  peroxide  should  be
stored according to manufacturer's directions.

     Potassium Iodide  Solution,  10 Percent - Dissolve 10.0 g of
potassium  iodide  in  water, and dilute to 100 ml.  Prepare when
needed.  This solution is used to check  for  peroxide impurities
in the isopropanol only.

     Drierite  - Anhydrous calcium sulfate (CaSO.)  desiccant,  8
mesh, indicating type is recommended.  Do  not  use silica gel or
similar desiccant in this application.  Manufacturer's specifica-
tions should be checked upon receipt.
                                                     o
     CO2  Absorber  -  Ascarite, Ascarite  II,  or  5A  molecular
sieve.  Ascarite or Ascarite  II  is  the  recommended absorption
media to collect the CO2  for  both  methods  because  it  is  an
indicating  type  of sorbant.  The indicating type  sorbant  will
provide a visual check  of whether the sorbant was spent prior to
the  completion of the run.  Ascarite may also be used  for  both
methods; the 5A molecular sieve may only be used  with the Method
6B constant rate sampling (low flow rate).  Because problems have
been detected with molecular sieve lots, it is necessary that new
lots   of  the  molecular  sieve  material  be  regenerated  upon
receipt.  This can be accomplished by placing the molecular sieve
in an oven  at  300 C for 4 hours and passing carbon dioxide-free
air through the molecular sieve (while it is in the  oven)  at  a
flow rate equal to the volume of molecular sieve per minute.  The
recommendedemolecular sieve material  is  Union Carbide 1/16-inch
pellets, 5 A or equivalent.   Note;  Ascarite may be a skin irri-
tant, and protection  should  be taken not to breath the Ascarite
dust.

1.4.2   Sample Recovery - The following are required  for  sample
recovery:

     Water  - Use deionized  distilled  water,  as  specified  in
Subsection 1.4.1.

     Isopropanol, 80 Percent (Method  6A)  - Mix 80 ml of isopro-
panol with 20 ml of water.

1.4.3    Analysis  -  The  following  are  required   for  sample
analysis:

-------
                                               Section No. 3.13.1
                                               Date July 1, 1986
                                               Page 14

     Water  -  Use  deionized distilled water, as  in  Subsection
1.4.1.

     Isopropanol, 100 Percent (Method 6A) - As specified above.

     Thorin Indicator - Dissolve 0.20 g of l-(o-arsonophenylazo)-
2-naphthol-3,  6-disulfonic  acid,  disodium  salt  in  100 ml of
water.

     Barium Perchlorate Solution,  0.0100N  -  Dissolve 1.95 g of
bariumperchloratetrihydrate(Ba(ClO4)2'3H?0)  in  200 ml  of
deionized distilled water and  dilute to 1 liter with 100 percent
isopropanol.  Alternatively, use 1.22 g of (BaC^ " 21^0) instead
of the perchlorate.  Standardize, as in Section 3.13.5.

     Sulfuric  Acid Standard, 0.0100N - Either purchase the manu-
facturer's certified or standardize the H^SO. at 0.0100N ^0.0002N
against 0.0100N NaOH that has been standardized  against  primary
standard grade potassium acid phthalate.

1.5   Analytical Equipment

     A spectrophotometer is needed  to  check the isopropanol for
peroxide impurities.  The  absorbance  is  read  at 352 nm on the
spectrophotometer.
o
                                                                    o
                                                                    o


-------
                                                                 Section No.  3.13.1
                                                                 Date July  1, 1986
                                                                 Page 15
                Table 1.1  ACTIVITY MATRIX FOR PROCUREMENT OF APPARATUS
                                     AND SUPPLIES
 Apparatus and
   supplies
   Acceptance limits
 Frequency  and method
   of  measurement
  Action if
requirements
are not met
 Sampling

 Sampling probe
  with heating
  system
 Capable of maintaining
 100° C  (212°F)  exit
 air at  flow rate  of
 1.0 L/min
Visually check and
run heating system
checkout
Repair or return
to supplier
 Out-of-stack
  filter
To  remove particulate
and to prevent  conden-
sation
As  above
As above
Flexible
 connector
 (optional)
To connect  the probe
to the midget bubbler
and to prevent conden-
sation
As above
As above
Midget bubbler/
impinger (large
impingers are
acceptable)
Standard stock glass
Visually check upon
receipt for breaks or
leaks
Return to manu-
facturer
CO- absorber
Minimum capacity of
150 g of Ascarite
Visually check upon
receipt for damage
and proper size
Return to
supplier
Vacuum pump
Capable of maintaining
flow rate of 1 to 2
L/min; leak free at
250 mm (10 in.) Hg
Check upon receipt
for leaks and
capacity
As above
Dry gas meter
(if required)
Capable of measuring
total volume within
2% at a flow rate of
1.0 L/min
Check for damage upon
receipt and calibrate
(Sec. 3.13.2) against
wet test meter
Reject if damaged,
behaves erratical-
ly, or cannot be
properly adjusted
Wet test meter
(if dry gas
meter required)
^continued)
Capable of measuring
total volume within
1%
Upon assembly, leak
check all connections
and check calibration
by liquid displacement
As above
                                                                         7

-------
Table 1.1   (continued)
                                                                Section No. 3.13.1
                                                                Date July 1, 1986
                                                                Page 16
                                                                   o
Apparatus and
  supplies
  Acceptance limits
 Frequency and method
   of measurement
  Action if
requirements
are not met
Rotameter
Within 5% of manufac
turer's calibration
curve (recommended)
Check upon receipt for
damage and calibrate
(Sec. 3.13.2) against
wet test meter
 Recalibrate and
 construct a new
 calibration
 curve
Thermometers
Within 1°C  (2°F)
of true value in the
range of 0°C to
25°C (32° to 77°F)
                 for impinger and +3
                 (5.4°F) for dry gas
                 meter thermometer

Check upon receipt
for damage (i.e., dents
and bent stem), and
calibrate (Sec. 3.13.2)
against mercury-in-
glass thermometer
 Return to
 supplier if un-
 able to cali-
 brate
Barometer
Capable of measuring
atmospheric pressure
to within 2.5 mm
(0.1 in.) Hg
Check against mercury-
in-glass barometer or
equivalent (Sec. 3-13.2)
 Determine cor-
 rection factor,
 or reject if
 difference is
 more than +2.5
                                                                                    O
Vacuum gauge
0 to 760 mm (0 to
29.92 in.) Hg range,
+25 mm  (1.0 in.) Hg
accuracy at 250 mm
(10 in.) Hg
Check against U-tube
mercury manometer
upon receipt
 Adjust or return
 to supplier
Industrial
timer (Method
6B only)
Properly operate pump
for specified sampling
cycle
Check the sample cycle
 Repair or reject
Sample Recovery
Wash bottles
Polyethylene or glass,
500-ml
Visually check for
damage upon receipt
 Replace or
 return to
 supplier
Storage bottles
(continued)
Polyethylene, 100-ml
Visually check for
damage upon receipt,
and be sure that caps
seal properly
 As above
                                                                                    O

-------
                                                                Section No. 3-13-1
                                                                Date July 1, 1986
                                                                Page 17
 Table  1.1  (continued)
Apparatus and
  supplies
 Acceptance limits
Frequency and method
    of measurement
  Action if
requirements
are not met
Balance
Accurate to +0.05g
for weighing impin-
gers and CO-
absorber
Check accuracy with
Class S weights
Repair or
reject
Analysis Glass-
ware

Pipettes,
volumetric
flasks, bur-
ettes , and
graduated
cylinders
Glass, Class A
Upon receipt, check
for stock number,
cracks, breaks, and
manufacturer flaws
As above
Reagents

Distilled
water
Must conform to ASTM-
D1193-74, Type 3
Check each lot or
specify type when
ordering
As above
Isopropanol
(Method 6A only)
100# isopropanol, re-
agent grade or certi-
fied ACS with no per-
oxide
Upon receipt, check
each lot for per-
oxide impurities
with a spectro-
photometer
Redistill or
pass through
alumina col-
umn, or re-
place
Hydrogen
peroxide
30% H202, reagent
grade or certified
ACS
Upon receipt, check
label for grade or
certification
Replace or
return to
manufac-
turer
Potassium iodide
solution
Potassium iodide,
reagent grade or cer-
tified ACS
As above
As above
Drierite
Anhydrous calcium sul-
fate (CaSOj.) desiccant,
8 mesh, indicating
type
Check manufacturer's
specification upon
receipt
Reject
(continued)

-------
Table 1.1 (continued)
                                                             Section No.  3.13.1
                                                             Date July 1,  1986
                                                             Page 18
                                                                              o
Apparatus and
  supplies
                   Acceptance limits
                        Frequency and method
                            of measurement
                         Action if
                         requirements
                         are not met
Ascarite or
Ascarite II
                  Capable of collecting
                  CO- for each sample
                  run
                           Check out each new
                           lot with known amount
                           of CO,,
                          Reject
Thorin indicator
                  1-(o-arsonophenylazo) •
                  2-naphthol-3,6-disul-
                  fonic acid, disodium
                  salt, reagent grade
                  or certified ACS
                           As above
                          As above
Barium perchlor-
ate solution
                  Barium perchlorate
                  trihydrate
                  (Ba(C104)2'3H20),
                  reagent grade or
                  certified ACS
                           As above
                          As above
                                                                              D
Sulfuric acid
Sulfuric acid,
0.0100N +0.0002N
Have certified by
manufacturer or stand-
ardize against 0.0100N
NaOH that has been
standardized against
potassium acid
phthalate (primary
standard grade)
As abov<
                                                                             O

-------
                                               Section No. 3.13.2
                                               Date July 1, 1986
                                               Page 1
 2.0   CALIBRATION OF APPARATUS
    Calibration of  the  apparatus  is  one of the most important
functions in maintaining data quality.  The  detailed calibration
procedures included in this section were designed  for the equip-
ment specified by Method  6  and  described  in the previous sec-
tion.  Table 2.1  at  the  end  of  this  section  summarizes the
quality  assurance  functions  for calibration.  All calibrations
should  be  recorded on standardized  forms  and  retained  in  a
calibration log book.

2.1  Metering System

    As previously stated,  the  metering  system  may  not be re-
quired.   For  Methods  6A  and 6B trains that  do  not  use  the
metering system, no calibration is required.

2.1.1  Wet Test Meter - The wet test meter must be calibrated and
have the proper capacity.  For  Methods  6A  and 6B, the wet test
meter should have a capacity of at least 2 L/min.  No upper limit
is placed on the capacity;  however, a wet test meter dial should
make at least one complete revolution at the specified  flow rate
for each of the three independent calibrations.

    Wet  test  meters  are  calibrated by the manufacturer to  an
accuracy of +0.5 percent.  Calibration of the wet test meter must
be checked initially upon receipt and yearly thereafter.

    The  following liquid positive displacement technique can  be
used to verify and adjust,  if necessary, the accuracy of the wet
test meter to +1 percent:

    1.    Level the wet test meter by adjusting the legs until the
bubble on the level located on the top of the meter is centered.

    2.    Adjust the water volume in the meter so that the pointer
in the water level gauge Just touches the meniscus.

    3.    Adjust  the  water manometer to zero by moving the scale
or by adding water to the manometer.

    4.    Set up the apparatus  and calibration system as shown in
Figure 2.1.

          a.   Fill the  rigid-wall  5-gal jug with water to below
              the air inlet tube,  and allow both  to  equilibrate
              to room temperature (about 24 h) before use.

          b.   Start  water  siphoning  through  the  system,   and
              collect the  water in a 1-gal container,  located in
              place of the volumetric flask.

-------
                                             Section No. 3.13.2
                                             Date July 1, 1986
                                             Page 2
                                                                   o
              AIR INLET
               TUBE
THERMOMETER
                                      LEVEL/
                                      GAUGE/

                                  WAFER OUT
33 VALVE
  OR PINCH CLAMP
                                              _|_ 2000-ML LINE
     CLASS A
     VOLUMETRIC
     FLASK
                                LEVEL ADJUS
O
Figure 2.1.  Calibration check apparatus  for  wet test meter.
                                                                   O

-------
                                               Section No. 3.13.2
                                               Date July 1, 1986
                                               Page 3

     5.    Check operation of the meter as follows:

           a.  If  the manometer reading is  <10  mm (0.4 in.) H.,,0,
              the meter is in proper working condition.  Continue
              to  step  6.

           b.  If  the manometer reading is  >10 mm (0.4 in.)  Ho0'
              the wet test meter is defective or  the  saturator
              has too much pressure drop.  If the wet test meter
              is  defective, return to the manufacturer for repair
              if  the   defect(s) (e.g., bad connections or joints)
              cannot be found and corrected.

     6.     Continue  the operation until the  1-gal  container  is
almost  full.   Plug   inlet to the wet test meter.   If  no  leak
exists, the flow  of liquid to the gallon container  should  stop.
If the flow continues, correct for leaks.  Turn the siphon system
off  by   closing  the  valve, and unplug the inlet to the wet test
meter.

     7.     Read  the  initial volume (V.) from the wet test  meter
dial, and record  on   the  wet test merer calibration log, Figure
2.2.

     8.    Place a  clean, dry volumetric flask (Class A)  under the
siphon  tube, open the pinch clamp, and fill the volumetric flask
to the mark.  The volumetric flask must be large enough  to allow
at least  one complete  revolution of  the  wet test meter with not
more than two fillings of the volumetric flask.     ,

     9.    Start the flow of water,  and record the maximum wet test
meter manometer reading  during the test after a constant flow of
liquid is  obtained.

     10.    Carefully fill the volumetric flask, and shut  off  the
liquid flow at the 2-liter mark.   Record the final volume on the
wet  test meter.

     11.   Perform  steps 7 through 10 three times.

     Since  the water  temperature in the wet test meter and reser-
voir has been equilibrated to the  ambient  temperature and since
the  pressure  in  the wet test meter will equilibrate  with  the
water reservoir   after the water flow is shut off, the air volume
can be compared directly with  the  liquid  displacement  volume.
Any  temperature  or pressure difference would be less than meas-
urement error and would not affect the final calculations.

    The   error should not exceed +_! percent;  should  this  error
magnitude be exceeded,   check  all  connections  within  the test
apparatus  for leaks,  and gravimetrically  check the volume of the


-------
         Wet test meter  serial  number
                                                                Date
         Range of wet  test meter flow rate Q— fZO


         Volume of test  flask Vg =    2~QOL~	

           Satisfactory  leak check?
           Ambient temperature  of  equilibrate liquid in wet test meter and reservoir
                                                                                          *F

Test
number
1
2
1
Manometer
reading, a
mm H20
6"
S
$-
Final
volume (V^),
L
Ml
2-00
2.W
Initial
volume (V^),
L
0
o
0
Total
volume (Vm) ,
L
/,??
^2.00
2.00
Flask
volume (Vs),
L
^.oo
Z.oo
2.0O
Percent
error,0
%
o. r
0
0
b

c
    Must be  less than  10 mm (0.4  in.)  H2O.
    Vm = vf - vi'

    % error =  100  (Vm -  VS)/VS
                                             (+1%).
                                     Signature of calibration person
                              Figure 2.2.   Wet test meter calibration log.
O
                                                  o
                                                                                                             •now
                                                                                                             cu o> CD
                                                                                                             tQ rt O
                                                                                                             <0 O rt-
                                                                                                                 H-
                                                                                                             it».C4 O
                                                                                                               C P
                                                                                                                 CO
                                                                                                               (-> •
                                                                                                               VO M
                                                                                                               03 CO
                                                                                                                 N)
o

-------
                                               Section No. 3.13.2
                                               Date July 1, 1986
                                               Page 5

standard  flask.  Repeat the calibration procedure,  and  if  the
tolerance level  is  not  met, adjust the liquid level within the
meter  (see the manufacturer's  manual)  until  the specifications
are met.

2.1.2   Sample  Metering  System - The sample  metering  system—
consisting  of  the  needle  valve,  pump, rotameter, and dry gas
meter—is initially calibrated  by  stringent  laboratory methods
before it is  used  in  the  field.   The calibration is then re-
checked  after  each field test series for Method 6A and every 30
days of operation for Method  6B.   This  recheck  requires  less
effort than the initial calibration.   When  a  recheck indicates
that the calibration  factor  has  changed, the tester must again
perform the complete laboratory procedure to obtain the new cali-
bration  factor.   After  the  meter is recalibrated, the metered
sample volume is multiplied by the calibration factor (initial or
recalibrated) that  yields  the  lower  gas  volume for each test
run.  Both sets of calibration results should be reported.

    Initial Calibration  -  The  metering  system should be cali-
brated when first  purchased  and  at any time the posttest check
yields a calibration  factor that does not agree within 5 percent
of the pretest calibration factor.  A calibrated  wet  test meter
(properly  sized, with +1 percent accuracy)  should  be  used  to
calibrate the metering system.

    The metering system should  be  calibrated  in  the following
manner before its initial use in the field.

    1.    Leak check the metering system (needle valve, pump, rot-
ameter, and dry gas meter) as follows:
                                                              3
    a.   Temporarily attach a suitable rotameter (e.g., 0-40 cm /m
        in)   to the outlet of the dry gas meter (for the 1  L/min
        sample train),  and place a vacuum gauge at  the  inlet to
        the sample train.  Alternatively,   for  trains  without a
        dry gas meter,  place the rotameter  at  the  discharge of
        the C02 absorber.

    b.   Pull a vacuum of at least 250 mm (10 in.) Hg.

    c.   Note  the flow rate as indicated by the rotameter for the
        1 L/min sample train or time the movement  of the dry gas
        meter needle for 2 minutes on the low flow train.

    d.   A leak of less than  2  percent of the appropriate sample
        rate must be recorded or leaks must be eliminated.

    e.   Carefully release the  vacuum  gauge  before  turning off
        pump.
                                                    U.;

-------
o
                                               Section No. 3.13.2
                                               Date July 1, 1986
                                               Page 6

    2.   Assemble the apparatus, as shown in Figure 2.3, with the
wet test meter replacing the C02  absorber  and  impingers; i.e.,
connect the outlet of the wet test meter to the inlet side of the
needle valve.

    3.    Run  the  pump for 15 minutes with the flow rate set at
1 L/min  to  allow the pump to warm up and to permit the interior
surface of the wet test meter to become wet.

    4.   Collect the information required  in the forms provided,
Figure 2.4A  (English units) or 2.4B (metric units), using sample
volumes equivalent  to  at least five revolutions of the dry test
meter.  Three independent runs must be made.

    5.   Calculate Y.  for  each  run  of  the  three  runs using
Equation 2-1.   Record  the  values  on  the form (Figure 2.4A or
2.4B).


               y  m Vw <*d + 460)  [Pm + (Dm/13.6)]   Equat±on 2_x

                1        Vd (tw + 460) Pm

where

 ,   Y. =   ratio for each run of volumes measured by the wet test
           meter and the dry gas meter, dimensionless calibration
           factor,

                                               3    3
    V  =   volume measured by wet test meter, m  (ft ),
     rw

    P  =   barometric pressure at the meters, mm (in.) Hg,

    D  =   pressure drop across the wet test meter, mm  (in.) H0O,
     in                                                        M

    t, =   average temperature of dry gas meter, °C (°F),

                                                  3    3
    V, =   volume measured by the dry gas meter, m  (ft  ), and

    t  =   temperature of wet test meter, °C (°F).

    6.   Adjust  and  recalibrate  or reject the dry gas meter if
one  or  more  values of Y. fall outside the interval  Y   +0.02Y,
where  Y  is  the  average  for  three  runs.   Otherwise,  the Y
(calibration factor) is acceptable  and  will  be used for future
checks and  subsequent  test  runs.  The completed form should be
forwarded to the supervisor  for  approval, and then filed in the
calibration log book.

    An alternative  method  of  calibrating  the  metering system     /"""\
consists of substituting a dry gas meter, which has been properly     f   j

-------
                                                    MANOMETER
                             THERMOMETER
SURGE TAN;
                                                           WATER IN
                                                                WATER LEVEL
                                                                GAUGE
WATER OUT

LEVEL ADJUST
V O W
0) 0> CD
 rt
        Figure 2.3.   Sample metering system calibration setup.
                                                                                 \O I-1
                                                                                 03 CO
                                                                                 o> •
                                                                                  to

-------
Date  /— ZS~— gS"   Calibrated by   £-£S

Barometer pressure, Pn =
                                                    Meter box number
                                                                                   Wet test meter number
                                       in. Hg   Dry gas meter temperature correction  factor
Wet test
meter
pressure
drop
"V'*
in. 820
tf.25T
0.25"
o.zs
Rota-
meter
setting

8Z
sf
Dry test meter
Outlet
gas temp
(V-
°F
78
60
00
Average
gas temp
(td),c
°F
71
e/
82.
Time
of run
(9),d
min
3o
3o
3o
Average
ratio
(Yi),e
/.0/r
•/.o/1
I.OI&
(Yri),f
I.6ZZ
1.62-Ce
/•030
a

b
 Dm expressed as negative number.

 Volume passing through meter.  Dry gas volume is minimum for at least five  revolutions  of  the meter.

 The average of td  and t,  if using two thermometers; the actual reading  if using one thermometer.

 The time it takes to complete the calibration run.

 With Y defined as the average ratio of volumes for the wet test and the dry test  meters, Y.  = Y  +0-.02

 calibration and Y.  = Y ^0.05 Y for the posttest checks; thus,
                                                                                                         Y for
    Vw (td+-460°F) [Pm+ (Dm/13.6)]


        Vd (tw + 460°F) (Pm)
                                        (Eq.  1)
                                                    and
'••-.•  Y
                       2)
 With Yr defined as the average ratio of volumetric measurement by wet  test meter to rotameter.

 Tolerance Yr = 1 j<).05 for calibration and Y +0.1 for posttest checks.
      w (td + 460°F) [Pm H- (Dm/13.6)]


       9 (tw + 460°F) (Pm) (Rs)
                                        (Eq.  3)
                                                      and
=   1.02-b .
                                         4)
               Figure 2.4A.  Dry gas meter calibration data form  (English units),
                                                                                                               »d D OT
                                                                                                               WOO)
                                                                                                              «3 ri- O
                                                                                                               0> (D rt
                                                                                                                   H-
                                                                                                               03 ti O
                                                                                                                 C 3
  O
M •
^

  03
M •
vO l-«
CO O)
cn •
  10
O
                                                     O
                                                                                                         O

-------
Date  /-Z$~-65      Calibrated by

                            746
Barometer pressure, P  =
                                                     Meter box  number   ^- ~~(pWet  test meter number  A-*/ ~~n~
                              in. Hg   Dry gas meter temperature  correction  factor  ///7
Wet test
meter
pressure
arop
'a
nun H2O
£.4
6,f
£.f
Rota-
meter
setting

Z7
2-1
Average
gas temp

-------
                                               Section No. 3.13.2
                                               Date July 1, 1986
                                               Page 10

prepared as a calibration standard, in  place  of  the  wet  test  I)
meter.   This  procedure  should  be  used  only after  obtaining
approval of the Administrator.

     Posttest  Calibration Check - After each field  test  series
for Method 6A and after every 30 days of operation for Method 6B,
conduct a calibration  check  as  in  Subsection  2.1.2  with the
following exceptions:

     1.  The leak  check  is  not conducted because a leak should
not be corrected that was present during testing.

     2.  Three or more revolutions of the dry  gas  meter  may be
used.

     3.   Only two independent runs need be made.

     4.   If a temperature-compensating  dry  gas meter was used,
the calibration  temperature for the dry gas meter must be within
6 C (10.8 F) of the average meter temperature observed during the
field test series.

     When  a  lower  meter  calibration  factor  is obtained as a
result of an uncorrected leak, the tester should correct the leak
and then determine the calibration  factor  for the leakless sys-   ^^^
tern.  If the new calibration factor changes the compliance status  fj
of the facility in comparison to the lower factor, either include  \	/
this information  in the report or consult with the administrator
for reporting  procedures.   If  the  calibration factor does not
deviate  by  >5  percent from the initial  calibration  factor  Y
(determined in Subsection 2.1.2), then the  dry gas meter volumes
obtained  during  the test series are acceptable.  If  the  cali-
bration factor does deviate by >5 percent, recalibrate the meter-
ing system as in Subsection 2.1.2, and for the calculations,  use
the calibration factor (initial or recalibration) that yields the
lower gas volume for each test run.

2.2  Thermometers

     The thermometers  used  to  measure  the  temperature of gas
leaving  the  C02 absorber should be initially  compared  with  a
mercury-in-glass thermometer that meets  ASTM  E-l No. 63C or 63F
specifications:

     1.   Place both the mercury-in-glass and the dial type or an
equivalent thermometer  in  an  ice  bath.   Compare the readings
after the bath stabilizes.
     2.   Allow both thermometers  to  come  to room temperature.
Compare readings after both stabilize.
                                                                   o

-------
                                               Section No. 3.13.2
                                               Date July 1, 1986
                                               Page 11

    3.   The dial type or equivalent thermometer is acceptable if
values agree within 1C (2 F) at both points.   If the difference
is  greater  than  1C  (2 F),  either  adjust or recalibrate the
thermometer until the above criteria are met, or reject it.

    4.   The thermometer is used as an indicator  and accuracy of
readings is not important for field use.

    The thermometer(s) on the dry gas meter inlet used to measure
the  metered sample gas temperature should be initially  compared
with a mercury-in-glass  thermometer  that meets ASTM E-l No. 63C
or 63F  specifications  (if the dry gas meter is required, other-
wise, no calibration is required):

    1.   Place the dial type or an equivalent thermometer and the
mercury-in-glass thermometer in a hot water  bath,  40   to  50 C
(104  to 122 F).  Compare the readings after the bath stabilizes.
                                                       i
    2.   Allow both thermometers  to  come  to  room temperature.
Compare readings after the thermometers stabilize.

    3.   The dial type or equivalent thermometer is acceptable if
values agree  within  3 C  (5.4 F)  at both points (steps 1 and 2
above)  or  if  the temperature differentials at both points  are
within 3 C (5.4°F)  and  the temperature differential is taped to
the  thermometer  and  recorded  on  the  meter  calibration form
(Figure 2.4A or 2.4B).

    4.   Prior to each field trip, compare  the temperature read-
ing of the mercury-in-glass  thermometer at room temperature with
that of the thermometer that is part of the meter system.  If the
values  or  the  corrected  values are not within 6 C (10.8 F) of
each other, replace or recalibrate the meter thermometer.

    5.  The thermometer must be recalibrated only when the volume
metering system does not pass the posttest calibration.

2.3  Rotameter

    The Reference Method  does  not require that the tester cali-
brate  the  rotameter.  The rotameter should be cleaned and main-
tained according to the manufacturer's  instructions.   For  this
reason, it is recommended that the calibration curve and/or rota-
meter markings be checked upon receipt and then routinely checked
with the posttest meter system check or at the required frequency
for the posttest meter check  when  a  dry gas meter is not used.
The rotameter may be calibrated as follows:

    1.   Ensure that the rotameter has been cleaned as  specified
by the manufacturer, and is not damaged.
                                                  s
7.

-------
                                               Section No.  3.13.2
                                               Date July 1, 1986
                                               Page 12

    2.   Use the manufacturer's calibration curve and/or markings
on the rotameter for the initial calibration.  Calibrate the rot-
ameter as described in the meter system calibration of Subsection
2.1.2, and record the data on the calibration form  (Figure  2.4A
or 2.4B).

    3.    Use the rotameter for testing if the pretest calculated
calibration is within  the  range  1.0 +0.05 L/min.  If, however,
the  calibration  point  is not within 5 percent, determine a new
flow rate setting, and recalibrate the  system  until  the proper
setting is determined.

    4.   Check the rotameter calibration with each posttest meter
system check.  If the rotameter check is within 10 percent of the
1-L/min  setting,  the rotameter can be  acceptable  with  proper
maintenance.   If, however, the check is not within 10 percent of
the flow setting, disassemble and clean the rotameter and perform
a full recalibration.

2.4  Barometer

    The field barometer should be adjusted initially  and  before
each  test  series  to  agree  within  2.5 mm (0.1 in.) Hg with a
mercury-in-glass barometer  or  with  the pressure value reported
from a nearby National Weather Service Station  and corrected for
elevation.  The tester should be aware that the pressure readings
are  normally  corrected to sea level.  The uncorrected  readings
should be obtained.  The correction for the elevation  difference
between the weather station  and  the  sampling  point  should be
applied at a rate of -2.5 mm Hg/30m (-0.1  in.  Hg/100  ft)  ele-
vation increase, or vice versa for elevation decrease.

    The calibration checks should be recorded on the pretest sam-
pling form (Figure 2.5).

2.5  Balance

    The balance must  be  checked  prior to each series of weigh-
ings, but not more  than once a day.  Place the CO2 absorber or a
midget  impinger on the balance.  Record the weighr.  Place a 5 g
Class  S  weight  on  the  balance  and  record the weight.   The
difference must be 5.0 +_ 0.1 g or the balance  must  be adjusted,
repaired, or rejected.
          o
,
          O

-------
                                               Section No. 3.13.2
                                               Date July 1, 1986
                                               Page 13

Date    /£>/Z*>/e>5~	    Calibrated by    &£S	
Meter box number    £~(s	


Rotameter

Pretest calibration factor (Y ) acceptable?    \S yes  	no
  (within 10 percent of correSt value).

                             *
Dry Gas Meter (If applicable)

Pretest calibration factor (Y) =   /.O2.1    (within 2 percent of
  average factor for each calibration run).

Gas Meter Thermometer (If applicable)

Temperature correction necessary?  	yes  __^_no
  (within 3 C (5.4 F) of reference values for calibration and
  within 6 C (10.8 F) of reference values for calibration
  check).

If yes,  temperature correction 	

Barometer

Field barometer reading correct?   r  yes 	no
  (within 2.5 mm (0.1 in) Hg of mercury-in-glass barometer).


Balance

Was the pretest calibration of the balance correct?  ^yes 	 no
  (within 0.05 g of true value using Class S weights).
*
  Most significant items/parameters to be checked.
               Figure 2.5.   Pretest sampling checks,

-------
                                              Section No. 3.13.2
                                              Date July 1, 1986
                                              Page 14
                                                                                   o
              Table 2.1.  ACTIVITY MATRIX FOR CALIBRATION OF EQUIPMENT
  Apparatus
 Acceptance limits
Frequency and method
    of measurement
  Action if
requirements
are not met
Wet test meter
Capacity of at least
2 L/min and an accur-
acy within 1.0%
Calibrate initially and
then yearly by liquid
displacement
Adjust until
specifications
are met, or
return to man-
ufacturer
Dry gas meter
Y  = Y^0.02Y at a
flow rate of about
1 L/min
Calibrate vs. wet test
meter initially and when
the posttest check is
not within Y+0.05Y
Repair and
then recali-
brate or re-
place
CO- absorber
thermometer
Within 1°C  (2°F)
of true value
Calibrate each ini-
tially as a separate
component against a
mercury-in-glass ther-
mometer
Adjust, deter-
mine a con-
stant correc-
tion factor,
or reject
                                                                                   O
Dry gas meter
thermometer
Within 3°C  (5.4°F)
of true value
Calibrate initially
and recalibrate when
the meter system
does not pass the
posttest check
As above
Rotameter
Clean and maintain
according to manu-
facturer's instruc-
tions (required);
calibrate to *_ 5%
(recommended)
Initially and after
each field trip for
Method 6A and every
30 days of operation
for Method 6B
Adjust and re-
calibrate, or
reject
Barometer
^2.5 mm (0.1 in.)
Hg of mercury-in-
glass barometer or
of weather station
value
Calibrate initially
using a mercury-in-
glass barometer; check
before and after each
field test
Adjust to agree
with certified
barometer
Balance
Weigh impinger
and COy absorb-
er to + 0.1 g
Check prior to each
series of weighings
Adjust to agree,
repair, or
reject
                                                                        /•'

-------
                                               Section No. 3.13.3
                                               Date July 1, 1986
                                               Page 1
 3.0    PRESAMPLING OPERATIONS
     The  quality  assurance  activities for presampling  preparation
 are  summarized in  Table  3.1  at  the  end  of this section.  See
 Section  3.0 of this  Handbook  for  details  on  preliminary site
 visits.

 3. 1  Apparatus Check and Calibration

     Figure 3.1 or  a similar form is recommended to aid the tester
 in preparing  an  equipment checklist,  status  report  form, and
 packing  list.

 3.1.1  Sampling  Train  -  The schematic of the SO2 train is given
 in  Figure  1.1.   Commercial models of this system are available.
 Each individual  or fabricated  train  must  be in compliance with
 the  specifications in the  Method, Section 3.5.10.

 3.1.2  Probe  - The probe should be cleaned internally by brushing
 first  with tap  water, then with deionized distilled  water,  and
 finally  with  acetone.  Allow probe to dry in the air.  In extreme
 cases,   the   glass or  stainless steel liner can be cleaned with
 stronger reagents; the objective is to leave the liner free from
 contaminants.  The probe's heating  system  should be checked to
 see  that it is operating properly.  The probe must  be  leak free
 when sealed at the inlet or tip and checked for leaks at a vacuum
 of 250 mm (10 in.)  Hg  with  the meter box.  Any leaks should be
 corrected.  The  liner should be sealed inside the metal sheath to
 prevent  diluent   air  from entering the source since most stacks
 are  under negative pressure.

 3.1.3  Midget Bubblers, Midget Impingers, and Glass Connectors -
     All  glassware  should be cleaned with detergent and tap water,
 and  then with deionized distilled water.   Any  items that do not
pass a visual inspection   for cracks or breakage must be repaired
or discarded.

3.1.4  C02 Absorber - The  cylinders or bottles may be packed with
the  Ascarite, numbered, weighed, and sealed  in  the  laboratory
prior  to  the field trip.   If molecular sieve material is  used,
ensure that it has been  regenerated  as  described in Subsection
 1.4.1.

3.1..  5  Valve and Rotameter - Prior to each field trip  or  at any
sign of erratic  behavior,   the  flow control valve and rotameter
should be cleaned  according to the maintenance  procedure  recom-
mended by the manufacturer.

3.1.6  Pump -  The vacuum pump  and  oiler  should  be serviced as
recommended by the  manufacturer, every 3 months, or upon erratic
behavior (nonuniform or insufficient pumping action).

-------
                                               Section No. 3.13.3
                                               Date July 1, 1986
                                               Page 2
Apparatus check
Probe
Type liner
Glass X
Stainless
steel
Other
Heated properly
Leak checked on
sampling train
Filter or Filter
Assembly
Glass wool X
Other

Glassware
Midget bubbler
Midget impinger
Size rJ/A
Type MM
•
Meter System
With timer
Without timer j< 	
Leak- free pump*
Rate meter*
Dry gas meter*
Reagents
Distilled water
H202, 30%
isopropanol, 100%*
(for Method 6A)
Drierite
Ascarite X"
or 5A molecular
sieve*

Other
Barometer
C02 absorber
column
Balance
Acceptable
Yes
/
S
l/
v/
S
v/
I/
S
•"
•/
^
\S
S
S
\s
s
No






Quantity
required
f
f 0l€f-~of-

-------
                                               Section No. 3.13.3
                                               Date July 1, 1986
                                               Page 3

3.1.7   Dry Gas Meter - A dry-gas meter calibration check  should
be made in accordance with the procedure in Section  3.13.2.    An
acceptable posttest check from the previous test is sufficient.

3.1.8  Thermometers -  The  thermometers  should be compared with
the  mercury-in-glass  thermometer  at room temperature prior  to
each field trip,             ;

3.1.9  Barometer  -  The  field barometer should be compared with
either  the  mercury-in-glass barometer  or  a  National  Weather
Service Station prior to each field trip.

3.1.10  Balance - Check balance with Class S weights using proce-
dures from Subsection 2.5 and pack in rigid foam container.

3.1.11  Other Sampling Apparatus - Other sampling equipment,  such
as Mae West bubblers and rigid cylinders for moisture absorption,
which require sample or reagent volumes  other  than those speci-
fied in this procedure for full effectiveness,  may  be used sub-
ject to the approval of the Administrator.

3.2  Reagents and Equipment

3.2.1  Sampling  - The midget bubbler solution.(for Method 6A) is
prepared by mixing  80 ml of isopropanol (100 percent) with 20 ml
of water.  Thexmidget impinger absorbing reagent  is  prepared by
diluting 100 ml of 30 percent  hydrogen  peroxide to 1 liter with
water for Method  6A or 250 ml of 30 percent hydrogen peroxide to
1 liter with water  for Method 6B.  All reagents must be prepared
fresh  for  each  test series, using ACS reagent grade chemicals.
Solutions containing isopropanol must be kept in sealed  contain-
ers to prevent  evaporation.   Twenty  five (25) g of Drierite is
needed for each sample collection.  Sufficient quantity should be
brought in a sealed container.

3.2.2  Sample Recovery - Deionized distilled water is required on
site for quantitative transfer of impinger  solutions  to storage
containers.   This  water  and  isopropanol are used to clean the
midget bubbler after testing and prior to taking another sample.

3.3  Packaging Equipment for Shipment

    Equipment should be packed in rigid containers  to protect it
against rough handling during shipping  and field operations (not
mandatory).

3.3.1  Probe - The inlet and outlet of the probe must  be  sealed
and protected from breakage.  A suggested container  is  a wooden
case  lined  with  polyethylene  foam  or other suitable  packing
material; the case should have separate compartments for individ-
ual devices.  The case should be equipped  with  handles  or  eye

-------
                                               Section No. 3.13.3
                                               Date July 1, 1986
                                               Page 4

hooks that can withstand hoisting, and should be rigid to prevent   (   )
bending or twisting during shipping and handling.                   ^—^

3.3.2   Midget  Bubblers,  Impingers,  Connectors,  and  Assorted
Glassware  -  All  bubblers, impingers, and glassware  should  be
packed in a rigid container and protected by polyethylene foam or
other  suitable packing material.   Individual  compartments  for
glassware help to organize  and  protect each item.  The impinger
train may be charged and assembled in the laboratory if  sampling
is to be performed within 24 hours.

3.3.3  COg  Absorber and Volumetric Glassware - A rigid container
lined  wirhpolyethylene foam material protects C02 absorber and
assorted volumetric glassware.

3.3.4   Meter  Box  - The meter box (if required)—which contains
the  valve,rotameter,  vacuum pump, dry gas meter, and thermom-
eters—should bo packed in a rigid shipping container  unless its
housing is strong enough  to  protect  components  during travel.
Additional  pump  oil  should  be  packed  if oil is required for
operation.  It is advisable to ship a spare meter  box in case of
equipment failure.

3.3.5  Wash  Bottles  and Storage Containers - Storage containers
and miscellaneous glassware may bo safelytransported, if packed
in a rigid foam-lined  container.   Samples  being transported in   /"""N
the  containers should be protected from extremely  high  ambient   (   j
temperatures (>50 C or about 120 F).                                ^-^


-------
                                                                Section No. 3.13-3
                                                                Date July 1, 1986
                                                                Page 5
                 Table 3.1.  ACTIVITY MATRIX FOR PRESAMPLING OPERATIONS
 Operation
 Acceptance limits
Frequency and method
    of measurement
Action if
requirements
are not met
Apparatus
Probe
1. Probe liner free
of contaminants
                  2. Probe leak free at
                  at 250 mm (10 in.) Hg

                  3. No moisture conden-
                  sation
1. Clean probe internal-
ly by brushing with tap
water, then deionized
distilled water, then
acetone; allow to dry in
air before test

2. Visual check before
test

Check out heating system
initialy and when mois-
ture appears during
testing
1. Retrace
cleaning pro-
cedure and
assembly
                                                    2. Replace
                                                    3. Repair or
                                                    replace
Midget bubbler,
 midget impin-
 ger, CO- ab-
 sorber, and
 glass con-
 nectors
Clean and free of
breaks, cracks, etc.
Clean with detergent,
tap water, and then
with deionized dis-
tilled water
Repair or
discard
Flow control
 valve and
 rotameter
Clean and without sign
of erratic behavior
(such as ball not
moving freely)
Clean prior to each
field trip or upon
erratic behavior
Repair or
return to
manufacturer
Vacuum pump
Maintain sampling rate
of about 1 L/min up
to 250 mm (10 in.) Hg
Service every 3 mo or
upon erratic behavior;
check oiler jars every
10th test
As above
Dry gas meter
(if required)
Clean and within 2%
of calibration factor
Calibrate according to
Sec. 3.13.2; check for
excess oil if oiler is
used
As above
Balance


(continued)
Accurate to within
0.1 g
Check with Class S
weights
As above

-------
                                                                Section No. 3-13-3
                                                                Date July 1, 1986
                                                                Page 6
Table 3.1.  (continued)
                                                                o
 Operation
 Acceptance limits
Frequency and method
    of measurement
  Action if
  requirements
  are not met
Reagents

Sampling
1. Requires all ACS
grade reagents
                  2. New C02
                  absorber material
1. Prepare fresh daily
and store in sealed
containers

2. Purchase new
1.  Prepare new
reagent
                                                  2. Reorder
Sample recovery
Requires deionized
distilled water on
site
Use water and reagent
grade isopropanol to
clean midget bubbler
after test and before
sampling
Prepare new
reagent
Package Equip-
ment for Ship-
ment

Probe
Protect with poly-
ethylene foam
Prior to each ship-
ment
Repack
O
Midget bubbler,
 impingers, con-
 nectors , and
 assorted glass-
 ware
Pack in rigid con-
tainers with poly-
ethylene foam
As above
As above
C0? absorber,
 volumetric
 glassware
Sturdy container
lined with foam
As above
As above
Meter box
Meter box case and/or
container to protect
components; pack spare
meter box and oil
As above
As above
Wash bottles
 and storage
 containers
Pack in rigid foam-
lined container
As above
As above
Balance
Pack in rigid foam-
lined container
As above
As above
                                                                                 O

-------
                                               Section No. 3.13.4
                                               Date July 1, 1986
                                               Page 1
 4.0  ON-SITE MEASUREMENTS
     On-site activities may include transporting the equipment to
the  test  site, unpacking and assembling,  sampling  for  sulfur
dioxide and carbon dioxide analyses, and recording  the data.  In
general  for  Method  6B, the equipment would be maintained at or
near the test site and testing would be on a more  routine basis.
Since  Method 6B is used to determine a daily average, facilities
should consider running duplicate Method 6B sampling trains.  One
Method  6B sampling train would be designated as the primary  and
the other would be the backup train.  This would prevent the loss
of  data, provide a check of sampling problems, provide  sampling
precision data, and provide  a  complete backup sample system for
when  the  primary train is inoperable.  The additional  manpower
requirements  should not be  significant  when  compared  to  the
possible  gain  in emissions data recovery.  The on-site  quality
assurance  activities  are  summarized in Table 4.1 at the end of
this section.

4.1  Transport of Equipment to the Sampling Site

     The most efficient means of transporting the  equipment from
ground level  to  the  sampling  site  (often above ground level)
should be decided during the preliminary  site  visit or by prior
correspondence.  Care should  be  taken  to prevent damage to the
equipment or injury to  test  personnel  during  the  moving.   A
laboratory type area should  be designated for preparation of the
absorbing  reagents,   for charging of the bubblers and impingers,
and for sample recovery and analyses.

4.2  Preliminary Measurements and Setup

     The Reference Method  outlines  the procedure used to deter-
mine  the  concentration  of sulfur dioxide in the gas stream  in
terms  of pounds of sulfur dioxide per million Btu's.  The  accu-
racy  of  the  equipment after transport to the sampling site and
possible  rough  handling can be determined by making a one-point
check of the rotameter reading  against the dry gas meter reading
at the test  site.   Use  Equation  3  in Figure 2.4A or 2.4B and
substitute  dry  gas  meter  readings  in place of wet test meter
readings  (i.e.,  Vd  = V ).  The value Y . should be between 0.9
and  1.1;   if  not,   the  meter  box has lost its rate or  volume
calibration.  The tester can  still  use  the  meter box, but the
data should not be released for decision  making until a posttest
recalibration  has  been  made.   If the dry gas meter calibration
factor  did  change,   the  dry gas meter volumes may have  to  be
corrected.   Record the test identification number  on  the appro-
priate sampling form,  Figure 4.1 (for Method 6A)  or  Figure  4.2
(for Method 6B).

-------
                    ro
Plant name
Sample location   $
                                       tta
                                                               Section No. 3.13.4
                                                               Date July 1, 1986
                                                               Page 2
City
Date
                                                                                   o
                                                       /   '
                                            Sample number
Probe length m J^tT_
Probe heater setting  	
Meter calibration factor (Y)
Sampling point location I3$t*\
Sample purge time, min
Remarks
                                                                          '/""

Sampling
time,
min
0
$•
/O
l£
2o
2£

Total
z£
Clock
time,
24 h
not
iio£
it to
Illb
II2D
/US'


Sample
volume,
L &?]
IZ0.2-0
IZS'.ZO
130. 10
/3S.20
140. Zb
14-5.20

Total
J^.OO
Sample
flow rate
setting,
L/min
4^/n±nf
— •
1-0
Lo
LO
ID
i.o


Sample
volume
metered
L^i
	
S.I
4-6
&
&o
6~.0

Vm Z.D
avg
Percent
deviation,
%
— -
z
4-
Z
0
0

Avg y /
dev A^
Dry gas
meter
temp ,
°c^7
. —
Zl
23
3o
50
50

Avg
z<\
Impinger
temp,
°c&r
—
n
2o
^0
to
to

Max
temp^--^
                                                                                   O
a Percent deviation =   m "   m avg   x 100  (must be within  10 percent)
                            Vm avg

                Figure 4.1.  Field sampling  data form for Method  6A.
                                                                                   O

-------
                                               Section No. 3.13.4
                                               Date July  1,  1986
                                               Page 3
PC
Plant 	
Sample location
Operator
Run No.
              orte*-
                    ?>/**-(-
                      Ak. 3
Sampling period
Dry Gas Meter
Final reading  744.
                   Start:
                   Stop:
Date
Date
Initial leak check
Final leak check   2
Recovery date
Recovered by
  /Q/fi/Bf
                         6>stU/
                                                          t«»<-
                                                  tpn*i
                                    6l3>l &S~
                                      Time
                                      Time
Initial reading 7/^.32. L
Volume metered   27.02- L
Dry Gas Meter Calibration Factor, Y
     Rotameter
     Initial setting
     Final setting
                                          L  or cc/min
                                          L  or cc/min
                                       /.£/7
Meter Temperature
                                 Barometric Pressure
73
/O'.^O,
Probe Temperature
Initial /OO F
Final 100 °F
°F
^n time
Filter Temperature
Initial /2.0 °F
Final 12~O °F
2*?. 73 in. Hg
/ ' O : ^-S~^ii\ time
Ascarite Column
Final wt 3/ 2. / g
Inital wt 303. (f g
Net wt 8-5"" g of CO,
Moisture


Final wt

Initial wt

Net wt
           1st bubbler    2nd impinger   3rd impinger   4th bubbler
/3./ g
73.1 g
0 •() g
Total moisture
07.3 g
oV^.O g
2.O g
3-6
&o.^>
68-2-
6.1
g
g
g
g
.20
7to. r g
93~-2- g
/•^" g
% spent
                     RECOVERED SAMPLE (If Applicable)
     H2°2
     container no.
                      AP"
     Impinger contents
     container no.     AP~I
     H2O blank
     container no.    frf>-IV\J&
     Samples stored and locked
     Received by

     Remarks
         Liquid level

         marked
                                     Liquid level
                                     marked
                                     Liquid level

                                     marked
                                          Date
     Figure 4.2.
                  Method 6B sampling, sample recovery, and sample
                  integrity data form.

-------
                                               Section No.  3.13.4
                                               Date July 1,  1986
                                               Page 4
o
4.3  Sampling

     The on-site sampling includes the following steps:

     1.   Preparation  and/or  addition of the absorbing reagents
to the midget bubblers and impingers and C02 absorber.

     2.   Setup of the sampling train.

     3.   Connection to the electrical service.

     4.   Preparation of the probe (leak check of entire sampling
train and addition of particulate filter).

     5.   Insertion of the probe into the stack.

     6.   Sealing the port.

     7.   Checking the temperature of the probe.

     8.   Sampling.

     9.   Recording the data in Figure 4.1.

A final leak check of the train  is  always performed after samp- (   J
ling.                                                             ^^

4.3.1  Preparation  and/or Addition of Absorbing Reagents to Col-
lection System - Absorbing reagents can be  prepared  on site, if
necessary, according to the directions in Section 3.13.3.

     For Method 6A

     1.   Use a pipette  or  a graduated cylinder to introduce 15
ml of 80 percent isopropanol (IPA)  into  the  midget  bubbler or
into  a  graduated  impinger bottle.  Do not use the  pipette  or
graduated  cylinder  that  was  used to add the hydrogen peroxide
solution  without  cleaning.   Pipettes  or  graduated  cylinders
should be marked for use  of  H->Oo  or  IpA  to minimize any pos-
sibility  of  introducing hydrogen peroxide into the isopropanol.
The accuracy of a pipette is not required  but  may  be  used for
convenience.

     2.   Add 15 ml of 3 percent hydrogen peroxide to each of the
two midget impingers (100  ml  of 30 percent H202 to 1 liter with
water).

     3.   Pack  glass  wool  into  the  top  of  the first midget
bubbler  to  prevent  sulfuric acid mist from entering the midget
impingers and causing a high bias for SO.,.                        /*~NS

                                                                  u

-------
                                               Section No. 3.13.4
                                               Date July 1, 1986
                                               Page 5

     4.   Add about 25 g of Drierite to the last midget bubbler.

     5.    Calibrate  the balance  by  initially  placing  a  C02
absorber  or  midget  impinger  on  the balance and recording the
weight.  Then add a 5 g or 10 g Class  S  weight.  The difference
must be accurate to within 0.05 g.  (Calibrate only once a day.)

     6.   Weigh each impinger and bubbler, including contents, to
the nearest 0.1 g, and record the data on the sample recovery and
integrity form (Figure 4.3).

     7.   With  one end of the C02 absorber sealed,   place  glass
wool in the cylinder to a depth of about 1 cm.  Place about 150 g
of Ascarite II in the cylinder on top of the glass wool, and fill
the remaining space in the cylinder  with  glass  wool.  Assemble
the  cylinder  as  shown in Figure 4.4.  With the cylinder  in  a
horizontal  position,  rotate it around the horizontal axis.  The
C02 absorbing material  should  remain  in  position  during  the
rotation,   and  no open spaces or channels should be formed.   If
necessary, pack  more glass wool into  the cylinder  to  make the
CO- absorbing material stable.  Clean the outside of the cylinder
of loose dirt and  moisture, and weigh at room temperature to the
nearest  0.1  g.   Record  this  initial  mass  on the data  form
(Figure  4.3).  It is strongly recommended that a second, smaller
C02 absorber containing Ascarite  or Ascarite il be added in line
downstream of  the  primary  C02 absorber as a breakthrough indi-
cator.   Ascarite  II  turns  white when C02 is absorbed.  The C02
absorber may be pre-packed.

     For Method 6B

     1.   The  first midget bubbler remains empty or dry.  It  is
also  advisable to break off the stem to  prevent  the  solutions
from backing up into the probe.

     2.  Add 15 ml of X> percent hydrogen peroxide to each of the
two  midget impingers (250 ml of 30 percent H202 to 1 liter  with
distilled water).

     3.  Add about  25  g of Drierite to the last bubbler or more
to a cylinder.

     4.  Weigh each impinger  or  bubbler  including contents, to
the nearest 0.1 g and record the data  on  the  sample  data form
(Figure 4.2).  Note:  If large impingers  are  used more solution
should be added and more Drierite used.

     5.  With one end of the  C02  absorber  sealed,  place glass
wool in the cylinder to a depth of about 1 cm.  Place about 150 g
of Ascarite II in the cylinder on top of the glass wool, and fill
the remaining space in the cylinder  with  glass  wool.  Assemble

-------
                                                Section No.  3.13.4
                                                Date July 1,  1986
                                                Page 6
            1st bubbler  2nd impinger  3rd  impinger    4th bubbler

Final wt       Sf.y   g      ffr.g   g       66.4   g   	
Initial wt     ffr.2.   g      66.2-  g       07-f    g
                                                                     o
     Ascarite column:   Final wt     304-. 7 g

                        Initial wt   300>l  g
                        Net wt         f .(f  g of C02

                                           % spent
                          Recovered Sample
H2°2 blan^        LJ) i»n               Liquid  level
container no.    /Tr- //TP               marked
Samples stored and  locked

Remarks
Received by   yjJMjfl.  ftLUJL^	  Date
                   J
Remarks
Net wt       --0.3   q       2-.6  q       0-^   g       <9.£T
             Total moisture      3-3    g       /£>	   %  spent
Impinger contents      ,                 Liquid  level                  (   )
container no. 	Ar~l	            marked  	jX	    V_x

H20 blank                               Liquid  level
container no.      nP"lV(c>              marked
   Figure 4.3.  Method  6A  sample  recovery and integrity data form.
                                                                    O
                                                     oL-

-------
                                               Section No. 3.13.4
                                               Date July 1, 1986
                                               Page 7

the cylinder as shown in Figure 4.4.  With the cylinder in a hor-
izontal position, rotate it around the horizontal axis.  The  C0?
absorbing material should remain in position during the rotation,
and no open spaces or channels should be formed.   If  necessary,
pack more  glass wool  into  the  cylinder  to   make the CO,, ab-
sorbing material stable.  Clean the outside of  the  cylinder  of
loose  dirt  and moisture, and weigh at room temperature  to  the
nearest 0.1 g.  Record this initial mass on the data form (Figure
4.2).  If  Method  6B  is  to  be  operated  in a low sample flow
condition (less than 100 ml/min), molecular sieve material may be
substituted  for Ascarite  II  as  the  C02  absorbing  material;
however, 250 g of sieve material  should be used and it must have
been regenerated  prior  to use.  The recommended molecular sieve
material is Union  Carbide  1/16 inch pellets, 5&, or equivalent.
Molecular  sieve  material  need  not be discarded following  the
sampling run provided it is regenerated.  Use of molecular  sieve
material at flow rates higher than 100 ml/min may cause erroneous
CO, results.    It  is  recommended  that  a  second, smaller CO2
absorber  containing Ascarite II be added in line  downstream  of
the primary C02 absorber as  a  breakthrough indicator.  Ascarite
II  turns  whire  when CO2 is absorbed.  The CO2 absorber may  be
pre-packed, however molecular sieve must  be  weighed  the day of
testing.

4.3.2   Assembling  the Sampling Train  -  After  assembling  the
sampling train as shown in Figure 1.1, perform the following:

     1.   Ensure that the  CO~  absorber is mounted in a vertical
position with the entrance at the bottom to prevent channeling of
gases.

     2.   Adjust  probe  heater  to operating temperature.  Place
crushed ice and water around the impingers and bubblers.

     3.   Leak  check the sampling train Just prior to use at the
sampling site  (not  mandatory)  by temporarily attaching a rota-
meter (capacity  of  0 to 40 ml/min) to the outlet of the dry gas
meter and placing  a  vacuum  gauge  at  or near the probe inlet.
Plug the probe inlet,  pull a vacuum of  at  least 250 mm (10 in.)
Hg, and note the flow rate indicated by the rotameter.  A leakage
rate <2 percent of the average  sampling rate is acceptable.  The
Method 6B constant rate low flow sampling train (20 to 40 ml/min)
will  be  checked by placing a U-tube water manometer at or  near
the probe inlet.  A vacuum  of  at  least  20  in.  H2O should be
pulled; the sample  valve should be shut and then the pump should
be  turned off.  The system must not  lose  more  than  0.25  in.
vacuum in 2 minutes.    Note;   Carefully  release  the probe inlet
plug  before turning off the pump.  Observe the impingers  during
the leak check to ensure that none of the solution is transferred
to another  impinger  and  that the glass wool (if applicable) is
not wetted.   If this occurs,  the  impinger  section  of the train

-------
                                            Section No.  3.13.4
                                            Date July 1,  1986
                                            Page 8
                                            o
SAMPLE
 GAS
.RUBBER  STOPPER

      -GLASS WOOL
                                       ASCARITE
                                                 GLASS WOOL
                                                        RUBBER
                                                        STOPPER
                                                                   O
                                                          OUTLET
                  Figure 4.4.  C02 absorber.
                                                                  O
                                                   / S n

-------
                                               Section No. 3.13.4
                                               Date July 1, 1986
                                               Page 9

must be prepared again.  It is suggested (but not mandatory) that
the pump be leak checked separately, either prior to or after the
sampling  run.   If prior to the run, the pump leak  check  shall
follow the train leak check.  To leak check the pump, proceed  as
follows.  Place a vacuum gauge at the inlet  to the pump.  Pull a
vacuum of  250  mm  (10 in.) Hg.  Plug or pinch off the outlet of
the  flow  meter, and then turn off the pump.  The vacuum  should
remain stable for at least 30 seconds.

     4.    Place a loosely packed filter of glass wool in the end
of the probe, and connect the probe to the bubbler.  Alternately,
if the out-of-stack filter is used, it should  be packed prior to
attaching the probe filter assembly to the bubbler.

     5.   Other sampling equipment, such as Mae West bubblers and
rigid cylinders for moisture absorption, which requires sample or
reagent volumes other than  those specified in this procedure for
full  effectiveness, may be used subject to the approval  of  the
Administrator.  An example of an  alternative' sampling train used
successfully in the collaborative testing program   is  shown  in
Figure 4.5.

4.3.3  Sampling - For  Method 6A, the sampling shall be conducted
at a constant rate of approximately  1.0  L/min.   For Method 6B,
the sampling shall be conducted either (1) intermittently with at
least  12  equal  flows  (approximately 1.0 L/min), evenly spaced
sampling  collections  of  between  2 to 4 minutes over a 24-hour
period, or (2) continuously at a rate of between 20 to 40  ml/min
for the 24-hour period.   The  intermittent  Method  6B  sampling
method is the recommended system for Method 6B testing because it
uses  Method 6 sampling components.  The detailed procedures  for
each method are described below.

     Note:   For applications  downstream  of  wet  scrubbers,  a
heated out-of-stack filter (either  borosilicate  glass  wool  or
glass fiber mat) is necessary.   The  filter  may  be  a separate
heated unit or may be within the heated portion of the probe.  If
the filter is within the sampling probe, the filter should not be
within 15 cm of the probe inlet  or  any  unheated section of the
probe,  such  as the connection to the first SO2  absorber.   The
probe and filter should  be  heated  to  at least 20  C above the
source temperature, but not greater  than  120   C.   The  filter
temperature  (i.e.,  the sample gas temperature) should be  moni-
tored to assure the desired temperature  is maintained.  A heated
Teflon  connector  may  be  used to connect the filter holder  or
probe to the first impinger.

     Constant Rate Sampling for Method 6A - Sampling is performed
at a constant rate of approximately 1.0 L/min as indicated by the
rotameter during the entire sampling run.  The  procedure  is  as
follows:

-------
                                  HEATED
                                GLASS WOOL
                                  FILTER
               HEATED PROBE
Method 6A*
A - 15 ml of Isopropanol
B - 15 ml of 3% H202
C - 15 ml of 150 g of Drierite
E - approx 250 g of Ascarite
Method 6B
A -
B -
C -
D -
Empty
15 ml of >6%
15 ml of >6%
approx 150 g

H2°2
Ho°o
ol I
                     irierite
E - approx 150 g of Ascarite

* This Method 6A train was
  not used during collaborative
  testing.

(


il
j|

!
!i

(
A

!
ii
Ij
ij

) (
B

Ij
!
i!
ii
!)

J
C

MAE WEST IMPINGERS
                                                                 D
                                                            DRIERITE
                                                             COLUMN
THERMOMET
  =5
                                  CO 2
                                  ABSORBER
             NEEDLE VALVE
       DRY
   [   GAS
   V  METER
SURGE
TANK
                                   (optional) TIMER
                                                     T) a co
                                                     cu p (D
                                                     CQ rt O
                                                     (D CD ft
                                                         P-
                                                     M Q O
                                                     O C D
                           Figure 4.5.  Alternative sampling train.
                                                                                             VO M
                                                                                             OJ CO
                                                                                             cn •
    O
        o
                                  o

-------
                                               Section No. 3.13.4
                                               Date July 1, 1986
                                               Page 11

     1.   Place crushed ice and water around the impingers.

     2.   Record  the  initial  dry gas meter readings, barometer
reading, and other data as indicated in Figure 4.1.  Double check
the dry gas meter reading and check the midget bubbler to be sure
that no hydrogen peroxide has been allowed to siphon back and wet
the glass wool.

     3.   Position  the  tip  of the probe at the sampling point,
connect the probe to the bubbler, and start  the  pump.  Warning;
If the  stack  is under a negative pressure of >50 mm (2 in.) H!O
vacuum, the probe should be positioned at the sampling point, tne
sample pump started prior to probe connection, and then the probe
immediately  connected  to the impinger to prevent  the  impinger
solutions from being  siphoned  backwards  and  contaminating the
isopropanol and glass  wool.   Alternatively,  the first impinger
stem may be broken off and/or a check valve placed in the system.

     4.   Adjust  the  sample flow to a constant rate of approxi-
mately 1.0 L/min as indicated by the rotameter.

     5.    Maintain  this constant rate within 10 percent  during
the entire sampling run,  and take readings  (dry  gas meter; rate
meter;  and temperatures at the dry gas meter and the C02 absorber
outlet) at least every 5 minutes.  Add more ice during the run to
keep the temperature of the gases leaving the last impinger at 20
 C (68 F) or less.   Salt may be added to the ice  bath to further
reduce the temperature.

     6.   Refer to emission standards  for  minimum sampling time
and/or  volume.  (For example, the Federal  standard  for  fossil
fuel-fired steam generators specifies a  minimum sampling time of
20  minutes  and a minimum sampling volume of 20 liters corrected
to standard conditions.)  The total sample volume at meter condi-
tions should be approximately 28 liters (1 ft ).   Make  a  quick
calculation  near the end of the run to guarantee that sufficient
sample  volume  has  been drawn; if the volume  is  insufficient,
sample for an additional 5 minutes.

     7.   Turn off the pump at the conclusion of each run, remove
probe from the stack, and record the  final  readings.   Warning:
Again,  if the stack  is under a negative pressure, disconnect the
probe first, and turn off the pump immediately thereafter or have
the first impinger modified and a check valve added.

     8.   Conduct a leak check, as described in  Subsection 4.3.2
(mandatory).

     9.   If the train passes the leak check, drain  the ice bath
and purge the remainder of the train by drawing clean ambient air
through  the  system for 15 minutes at  the  sampling  rate.   To

-------
                                               Section No. 3.13.4
                                               Date July 1, 1986
                                               Page 12            >—v

provide  clean ambient air, pass  air through  a charcoal  filter ^—'
or through an extra midget impinger containing  15  ml  of 3 per-
cent H?02.   The  tester  may  opt  to  use  ambient  air without
purification or to use only a filter.  Note;  It is  important to
drain  or  remove  the ice and water to allow the isopropanol  to
warm.

     10.  If the train  fails the leak check, either void the run
or  use  an alternative procedure acceptable to the Administrator
to adjust  the  sample volume for leakage.  An alternative proce-
dure that may be acceptable to the Administrator  is described at
the end of this subsection.

     11.  Calculate the sampling rate during  the  purging of the
sample.  The sample volume ( V)  for each point should be within
10 percent of the average  sample  volume for all points.  If the
average of all points is within  the  specified limit, the sample
rate  is acceptable.   Noncompliance  with  the  +;10  percent  of
constant rate for a single sample should not have  a  significant
effect on the final results of  the test for noncyclic processes.
However,  the Administrator should be consulted as to the accept-
ability of the sample collection run results.

     12.  Change the particulate filter (glass-wool  plug) at the
end  of  each test since particulate buildup oh the probe  filter
may result in a loss of SO.-  due  to  reactions  with particulate
matter.                   z

     Intermittent Sampling  for Method 6B - Sampling is performed
at a rate of approximately 1.0 L/min as indicated  by  the  rota-
meter.  It is conducted  for  12  equally  spaced  intervals; the
sample collection  periods  are  2  to  4 minutes in length.  The
Method  6B  sample  train has the same sample train components as
the Method 6A sample train with the exception  of  an addition of
an industrial  timer  switch,  designed  to  operate  in the "on"
position from 2 to 4 minutes on a 2-hour repeating cycle or other
cycle specified in the applicable  regulation.  At a minimum, the
sample operation should include at least 12 equal, evenly  spaced
periods of sampling  per 24 hours and, for the amount of sampling
reagents  prescribed  in  this  Method, the total  sample  volume
collected  should be  between  25  and  60  liters.   The  sample
procedure is as follows:

     1.    Add  cold water to the container holding the impingers
until the impingers and bubblers  are  covered  on  at least two-
thirds of  their  length.  The impingers, bubbler, and their con-
tainer must be covered and protected from intense heat and direct
sunlight.  If freezing conditions  exist,  the  impinger solution
and the water bath must be protected.
                                                                  o

-------
                                               Section No. 3.13.4
                                               Date July 1, 1986
                                               Page 13

     2.   Record the initial dry gas meter readings, probe/filter
temperatures,  and other data as indicated in Figure 4.2.  Double
check the dry  gas  meter  reading  and  ensure  the impinger and
bubbler container has the proper amount of cold water and is pro-
tected from extreme heat or cold.

     3.   Position  the  tip  of the probe at the sampling point,
connect the probe to the bubbler, and  turn on the time and start
the  pump.  Warning; If the stack is under a negative pressure of
>50  mm  (2  in.) H2O, the probe  should  be  positioned  at  the
sampling  point,  tne  sample  pump turned on, and then the probe
immediately  connected  to the impinger to prevent  the  impinger
solutions from being  siphoned  backwards  and  contaminating the
system.   The first impinger must be modified by breaking off the
stem and adding a check valve.

     4.   Adjust  the  sample  flow to a constant rate of approx-
imately 1.0 L/min as indicated by the rotameter.

     5.    Observe  the  sample  train  operations until the con-
clusion  of  the  first  2- to 4-minute sample collection period.
Determine the  volume  of  sample  collected  and  make  a  quick
calculation  to  ensure  that the volume from the given number of
equal,  evenly spaced sample collection periods will be within the
specified sample volume (i.e., 25 to 60 liters).

     6.    During the 24-hour sampling period, record the dry gas
meter  temperature  and  barometric  pressure  one  time  between
9:00 a.m.  and 11:00 a.m.

     7.   At the  conclusion  of the 24-hour period, turn off the
timer and the sample pump,  remove  the  probe from the stack, and
record  the  final  gas  meter  volume  reading, the probe/filter
temperature and rotameter setting.

     8.   Conduct  a leak check as described in Subsection 4.3.2.
If a  leak  is found,  void the test run or use procedures accept-
able to the Administrator to adjust  the  sample volume for leak-
age.   An  alternative  procedure  that  may be acceptable to the
Administrator is included at the end of this Subsection.

     9.    Check the final probe temperature, filter temperature,
and total sample  volume  to  ensure  that  all systems are still
working properly.

     10.   For scrubbed units change the filter material  prior to
the next sample run to ensure that the collected materials do not
scrub the SO0.  For unscrubbed units change the filter weekly.
            
-------
                                               Section No. 3.13.4
                                               Date July 1, 1986
                                               Page 14

     Note;   Method 6B does not require a purge at the completion  (   )
of the sample run since the train does not include isopropanol.      —

     Constant Rate Sampling for Method 6B - Sampling is performed
at a constant rate of between 20 to 40 ml/min as indicated by the
rotameter during the entire  sampling  run.  Lower flow rates and
longer  sampling  intervals  have been more successful  for  some
applications.  The procedure is as follows:

     1.    Add  cold water to the container holding the impingers
until the impingers and bubblers  are  covered  on  at least two-
thirds of their length.  The  impingers  and  bubbler,  and their
container, must be covered  and  protected  from intense heat and
direct sunlight.  If  freezing  conditions  exist,  the  impinger
solution and the water bath must be protected.

     2.   Record the initial dry gas meter readings, probe/filter
temperature, and other  data  as indicated in Figure 4.2.  Double
check the dry  gas  meter  reading  and  ensure  the impinger and
bubbler  container  has  the proper amount of cold water  and  is
protected from extreme heat or cold.
     3.   Position  the  tip  of the probe at the sampling point,
connect the probe to the bubbler, and start  the  pump.  Warning;
If the stack is under a negative pressure of >50 mm (2 in.)  HoO'
the probe should  be positioned at the sampling point, the sample
pump turned on, and then the probe immediately connected  to  the
impinger to prevent  the  impinger  solutions from being siphoned
backwards  and contaminating  the  system.   The  system  may  be
modified as mentioned above.

     4.  Adjust the sample flow to a constant rate of  between 20
and 40 ml/min as indicated by the rotameter.   Maintain this con-
stant rate during the entire test.

     5.   During the 24-hour sampling period,  record the dry gas
meter temperature and the barometric  pressure  one  time between
9:00 a.m. and 11:00 a.m.

     6.   At the conclusion of  the  24-hour  period,   record the
rotameter setting, turn off the pump, remove the probe  from  the
stack  and  record  the  final  gas  meter volume reading and the
probe/filter  temperatures.   Warning;   Again,  if  the stack is
under a negative pressure, disconnect the  probe  first, and turn
off the pump immediately thereafter.

     7.   Conduct a leak check in the following manner.  Attach a
U-tube  water  manometer  to the inlet to the probe.  Turn on the
pump  and  pull  a  vacuum  of  20 in. H20.  After the vacuum has
stabilized, shut off  the  main  sample  valve and then the pump.
The  leakage  rate  must  be less than 0.25 in. over  a  2-minute
o
                                                                   o

-------
                                               Section No. 3.13.4
                                •I: ,,,?           Date July 1, 1986
                                               Page 15

period.   If the leakage rate is in excess of 0.25 in. H20,  void
the test run or use procedures acceptable to the Administrator to
adjust the sample volume.  An alternative procedure that  may  be
acceptable to the Administrator is included  at  the  end of this
Subsection.

     8.    Check  the final probe temperature, filter temperature
and total sample volume to ensure  that  all  systems  were func-
tioning, properly.

     9.   For scrubbed units change the filter  material prior to
the  next sample run to ensure that the collected  material  does
not  scrub  the S02.  For nonscrubbed  units  change  the  filter
weekly.

     10.  To conduct the next sample  run  repeat  all  the above
steps.

     Note:  Method  6B  does  not  require  a sample purge at the
completion of the sample run since the  train  does  not  include
isopropanol.

    Alternative Leak Check Procedure for Unacceptable Leak Rates-
The leak check procedure for Method 6A and intermittent Method 6B
require that a vacuum gauge be placed  at  the  probe inlet, a 10
in.  Hg  vacuum  be  pulled  on the system (as read on the vacuum
gauge), and that the leak rate be checked  with  a more sensitive
rotameter (0 -  40 ml/min).  This system provides a quick indica-
tion when the leak rate is  over  4  percent  (the rotameter ball
will be pegged).  It provides the actual value when the leak rate
is under 4 percent.   Thus,  these  procedures  and  equipment as
specified  do  not quantify  the  leakage  rate  greater  than  4
percent.

     In an effort to retain and make useful the maximum amount of
emissions data possible, the following alternative may be accept-
able  to the Administrator when an unacceptable leak rate is  de-
tected for the Method 6A and intermittent Method 6B trains.  This
alternative  procedure  should  be  approved by the Administrator
prior to its use.

     When  an unacceptable post test leak check is  detected  the
following procedure may be used  to  compensate for the leak rate
(for  Method  6A  and  intermittent Method 6B).   This  procedure
assumes that the leak occurred for  the  duration of the test run
and may bias the results high.

     1.   After the sample train leakage  rate ,is found to be un-
acceptable at 10 in. Hg, release the  vacuum in the proper manner
and shut-off the sampling train.

-------
                                               Section No. 3.13.4
                                               Date Ju
                                               Page 16
Date July 1,  1986 /~"\
   2.  If the emissions results are to be calculated in  terms of
ppm S02 or Ib S02/million  Btu  without  using the results of C0?
collected by the sampling train, the vacuum gauge must be left on
the inlet to the probe.  However, if the emissions results are to
be calculated in terms of Ib SC>2 per million Btu using the  grams
of C02  collected  in the sampling train, the vacuum gauge may be
placed  on  the  inlet  to  the  first  impinger of H-CU.  Alter-
natively, the gauge  may be left at the probe inlet; However, the
leakage correction may then compensate for leakage rates that  do
not affect the results in terms of Ib SO2/million Btu.

   3.   Turn on the pump, and pull a vacuum of  2 in. Hg as shown
by the vacuum gauge.

   4.   After the vacuum stablizes  determine  the  leak  rate by
measuring the volume on the dry gas meter for at least 2 minutes.

   5.   The leak rate will be used to  compensate  only  for  the
mass of S09 in comparison to  the  C09  as  shown in the equation
below.    z                          ^

                                                     Equation 4-1


   M                 M                Sampling Rate               \~^/
    S02(corrected) =  (SCX,)    Sampling Rate - Leak Rate

where

   M-.- ,      .  -,. = mass of S00 corrected to compensate
    S02(corrected)   fQr leakag| rate;

   Mqo             = mass of SO,, determined for sample
      2              analysis;

   Sampling Rate   = Sample volume divided by the sample time
                     (continuous sample methods), for the
                     intermittent method use 1.0 L/min; and

   Leak Rate       = leak rate determined by this alternative
                     procedure (metered leak volume divided by
                     the time checked).

     When an unacceptable posttest leak check is detected for the
constant rate Method 6B train,  the  following  procedure  may be
used to compensate for the leak rate:

     I.   After the sampling train leakage rate  is  found  to be
unacceptable at 10 in. of H~0, release the  vacuum  in the proper
manner and shut off the sampling train.
                   o


-------
                                                Section No.  3.13.4
                                                Date July 1,  1986
                                                Page 17

    2.    If  the emission results  are  to  be  calculated in terms  of
 ppm S02  or Ib S02/million  Btu  without   using  the  results  of C02
 collected by  the   sampling  train,   the U-tube manometer must  be
 left on  the inlet  to the probe.   However, if  the  emission results
 are to  be  calculated  in  terms of  Ib  S02/million Btu using the
 grams  of  C02 collected in the sampling train, the U-tube   mano-
 meter  may be placed on the inlet   to   the first impinger of  H202.
 Alternatively,  the manometer may be left  at  the probe  infer;
 however,  the leakage correction may then compensate  for leakage
 rates  that  do  not affect the results in terms of  Ib S0«/million
 Btu.                                                     *

  .3.    Attach a 10-ml graduated   pipette  with  a  "T"  and  a bulb
 with soap solution to the outlet  of the  dry gas meter.

    4.    Turn on the pump and pull a   vacuum  of  20 in.  of  H20  as
 shown  by the manometer.

    5.     After  the  vacuum  stabilizes,  start  a   bubble  up the
 pipette.                                                        ;

    6.    Time the movement of the  bubble  over  at least  1.0   ml  of
 the pipette with a stop  watch.    Use the integer markings  of the
 pipette.

    7.    The leakage  rate  will   be   determined  by  dividing the
.volume by the time.

   .8.     Use  Equation  4-1  to   determine  the  correction for the
 determined leakage rate.

 4.4 Sample Recovery

    The Reference Method requires  the  weighing and transfer  of th^
 impinger contents  and the connector washings  to a polyethy-  lene
 storage  container.   This weighing and transfer  should  be done  in
 the "laboratory"  area  to  prevent   contamination   of  the test
 sample.    ,                                                     -,

    After  completing  the leak check  (for Method  6B) or the  purge
 (for Method 6A), disconnect the impingers and transport  them   to,,
 the cleanup area.   The  contents   of  the midget bubbler (contains
 isopropanol for Method 6A only) may be discarded  after the  weight
 is  determined.   However,  it is  usually   advisable  to retain this
 fraction  until analysis is performed on the H2O_.   Analysis   of
 the isopropanol may be useful in  detecting  cleanup  or  samplings
 errors.    Cap off  the midget impinger section  with  the use   of
 polyethylene or equivalent  caps   before transport  to the cleanup
 area.

    The sample should be  recovered as  follows:              .     .:?/,

-------
4.5  Sample Logistics (Data) and Packing Equipment - The sampling
and sample  recovery  procedures  are followed until the required
                                               Section No.  3.13.4
                                               Date July 1,  1986
                                               Page 18

     1.   Allow the impingers and C02  absorber  to  come to room
temperature (- 20 C), which should take approximately 10 minutes.

     2.   If the balance has not  been  calibrated  or  has  been
moved  within  the  past 24 hours, calibrate it as  described  in
Subsection 4.3.1 prior to the weighing of the samples.

     3.    Wipe  the outside of the bubblers, impingers, and  C02
absorber.

     4.   Weigh the bubblers, the  impingers,  and  C02  absorber
separately, and  record their weights to the nearest 0.1 g on the
proper  data  sheet (Figure 4.3 for Method 6A and Figure 4.2  for
Method 6B).

     5.   Method 6A - Transfer the contents of the two  impingers
containing solution to a labeled, leak-free,  polyethylene sample
bottle.   Wash  the impingers and connection glassware with three
15  ml  portions  of  water.   Place the rinsings in  the  sample
bottle.  The contents of the midget bubbler may  be  discarded or
saved for analysis if problems  are  detected  in  the subsequent
analysis of SO2.

      Method 6B  -  Recover  the  sample contents from the midget
bubbler and the two midget impingers  containing solution.  Rinse  /•—\
the bubbler, impingers, and connecting glassware with three 15 ml  (   J
portions of water.  The impinger contents and rinsings  should be  >—/
transferred to a labeled, leak-free polyethylene sample bottle.

     Note;  The total rinse and sample volume should be less than
100 ml; a 100-ml mark can be placed on the  outside  of the poly-
ethylene sample bottle as a guide.  Alternatively,  if the sample
recovery  is conducted in the laboratory, the sample recovery may
be conducted directly into a 100 ml volumetric flask.

     Warning;  It has been demonstrated that the contamination of
the sample with Ascarite or Drierite will bias the results.

     6.   Place 100 ml of the absorbing reagent in a polyethylene
bottle, and label it for use as a blank  during  sample analysis.
An example sample label is shown in Figure 4.6.

     7.    Mark the liquid level on the  outside  of  all  sample
bottles,  and  ensure  that the caps are on tightly  providing   a
leak-free container.

     8.   Discard the Ascarite and Drierite material.
                                                                   O

-------
                                               .Section No. 3.13.4
                                               Date July 1, 1986
                                               Page 19
Plant /4<2#*ti?
Site &>ibr
f~»-
fit*. 3 o*+lri-
Date /P-/0~$S~
Front rinse
Back rinse
Solution ^~
Front filter
_ Back filter
fOOflJL
Volume: Initial 3£>
Cleanup vby,

£,&£>

City skfif iJk&*~£
I
Sample Type ^O^/CO^.
Run Number AP-I
Front solution
Back solution
Level marked
Final
/

V/

en
B
0)






               Figure 4.6.  Example of a sample label.
number  of  runs  are  completed.  Log all data on the Sample and
Sample  Recovery Data Form, Figure 4.3 (Method 6A) and Figure 4.2
(Method 6B).  If the bubbler, impingers, and connectors are to be
used  in  the  next  test,  they  should be rinsed with distilled
water, and the bubbler should  be  rerinsed with isopropanol (for
Method 6A only).  A  new  or recharged CO~ absorber column should
be inserted  into  the  sampling train,  fit the completion "of the
test:

     1.   Check all sample containers for proper labeling  (time,
date,  location,  number of test, and  any  pertinent  documenta-
tion).  Be sure that a blank has been 'taken. '

     2.   If data is to be  removed  from the source area, record
all data collected  during  the  field test in duplicate by using
data  forms  and a field laboratory notebook.  One  set  of  data
should be mailed to the base laboratory, and one given to another
team member or to the Agency.   Hand  carrying the other set (not
mandatory) can prevent a very costly and embarrassing mistake.

     3.   Examine all sample containers  and  sampling  equipment
for  damage,  and pack them for shipment to the base  laboratory,
being careful to label all shipping containers to prevent loss of
samples or equipment.

     4.    Make  a check of  the  sampling  and  sample  recovery
procedures using the data form,  Figure 4.7 (Method  6A) or Figure
4.8 (Method 6B).         •  ,               ;v'«   -  , ••-.'"'           -'

-------
                                               Section No. 3.13.4
                                               Date July 1, 1986
                                               Page 20
Sampling
                                                                  o
Bubbler and impinger contents properly selected, measured, and
 placed in proper receptacle?* _ r

Impinger Contents/Parameters

1st:  15 ml of 80 percent isopropanol _ iX
2nd:  15 ml of 3 percent ^2°2* _ —
3rd:  15 ml of 3 percent H202*
4th:  approx. 25 g of Drierite*
150 g of Ascarite in C02 absorber?*
Probe heat at proper level?
Crushed ice around impingers?
Pretest leak check at 250 mm (10 in.) Hg?
Leakage rate?
Probe placed at proper sampling point?               

Sample Recovery

                                        *
Balance calibrated with Class S weights?  	
Impingers cleaned and weighed to +0.1 g at room temp?
Contents of impingers and rinsings placed in polyethylene
 bottles?	
                   5E
Fluid level marked?  	
                                                        9F
C00 absorber cleaned and weighed to +0.1 g at room temp?
                                    "^   'T
Sample containers sealed and identified?
Samples properly stored and locked? 	
*Most significant items/parameters to be checked.

             Figure 4.7.  On-Site measurements for Method 6A.      v_x

-------
                                               Section No.  3.13.4
                                               Date July 1, 1986
                                               Page 21
Sampling
Impinger contents properly selected, measured,  and placed in
 impingers? _ X^

Impinger Contents/Parameters

1st:  Empty* _ X^
2nd:  15 ml of >6 percent H2O2* _ ^
3rd:  15 ml of >6 percent H0O0*  ___ X^
               _           z ^  -
4th:  Approx. 25 g of Drierite* _ X
Approx. 150 g of Ascarite II or 250 g 5A molecular sieve
  (continuous flow rate train only) in C02 absorber?* _ X'
Probe heat at proper level? _ _ X
Crushed ice around impingers?
Pretest leak check at 250 mm (10 in.) Hg? _ \s
Leakage rate? _ Q.Q
                  "' '    "''" ' """''
Probe placed at proper sampling point? _ {X
Flow rate intermittent at approximately 1.0 L/min?* _ X
Flow rate constant between 20 to 40 ml/min? _ A/I A
Posttest leak check at 250 mm (10 in.) Hg?* _ »X
Leakage rate? _ Q.C>
Sample Recovery

Balance calibrated with Class S weights?* 	
Impingers cleaned and weighed to ^0.1 g at room temp?
Contents of impingers and rinsings placed in polyethylene
  bottles? 	fX	
Fluid level marked?*
                                                         *s
C02 absorber cleaned and weighed to ^0.1 g at room temp?*
Sample containers sealed and identified?* 	*s
Samples properly stored and locked?* 	X
*Most significant items/parameters to be checked.
             Figure 4.8.  On-Site measurements for Method 6B

-------
                                                                Section No.  3.13.4
                                                                Date  July 1,  1986
                                                                Page 22
             Table 4.1.  ACTIVITY MATRIX FOR ON-SITE MEASUREMENT CHECKS
                                                                o
 Operation
 Acceptance limits
Frequency and method
    of measurement
  Action if
requirements
are not met
Preparation and/
  or addition
  of absorbing
  reagents
Method 6A.  Add 15 ml
80% isopropanol to
first midget bubbler,
15 ml of 3% H202
to two midget impin-
gers, approx 25 g of
Drierite to the last
bubbler, and 150 g of
Ascarite to column

Method 6B.  Leave first
bubbler empty, add 15
ml of >6% H20- to
the two midget impin-
gers, approximately
25 g of Drierite to the
last midget bubbler, and
150 g of Ascarite to
column
Prepare 3% H_02 fresh
daily; use pipette or
graduated cylinder to
add solutions
Reassemble
collection
system
                                           Prepare >6% H202
                                           fresh daily; use pipette
                                           or graduated cylinder to
                                           add solutions
                           Reassemble
                           collection
                           system
                                                                                  O
Assembling the
  sampling train
1.   Assemble to speci-
fications in Fig. 1.1

2.   A leakage rate <2%
of the average samp-
ling rate
1.  Before each sampling
                                           2.  Leak check before
                                           sampling (recommended)
                                           by attaching a rotameter
                                           to dry gas meter outlet,
                                           placing a vacuum gauge at
                                           or near probe inlet, and
                                           pulling a vacuum of >250
                                           mm (10 in.) Hg
1.  Reassemble
                           2.  Correct
                           the leak
Sampling
  (Method 6A
  constant rate)
1.  Method 6A
Within 1Q% of a
constant rate
1. Calculate % deviation
for each sample using
equation in Fig. 4.1
1. Repeat
the sam-
pling, or
obtain ac-
ceptance
from a rep-
resentative
of the Admin-
istrator
(continued)
                                                                 O
                                                                     v..

-------
         Table 4.1.  (continued)
                                                                         Section No. 3.13.4
                                                                         Date  July 1, 1986
                                                                         Page 23
          Operation
         Sampling
           (Method 6B
           intermittent)
 Acceptance limits
                           2.  Minimum accept-
                           able time is 20 min
                           and volume is 20
                           liters corrected to
                           STP or as specified
                           by regulation

                           3.  Less than 2% leak-
                           age rate at 250 mm
                           (10 in.) Hg
                           4.  Purge remaining
                           S0_ from isopropanol
1.  At least 12
equally and evenly
spaced intermittent
sample intervals at
about 1.0 L/min
                           2.  Sample time is
                           24 hours and the
                           acceptable sample vol-
                           ume is between 25
                           and 60 liters

                           3.  Less than 2% leak-
                           age rate at 250 mm
                           (10 in.) Hg
Frequency and method
    of measurement
                        2.  Make a quick cal-
                        culation prior to com-
                        pletion and an exact
                        calculation after com-
                        pletion
                        3.  Leak check after
                        sample run (mandatory);
                        use same procedure as
                        above

                        4.  Drain ice, and purge
                        15 min with clean air
                        at the sample rate
1.  Check the volume of
the first sample inter-
val and the total vol-
ume should be within
10% of first sample
volume times the number
of intervals
                        2.  Make a calculation
                        after each sample run
                        3.  Leak check after
                        sample run (mandatory)
  Action if
requirements
are not met
                          2. As above
                          3.  As above
                          4.  As above
1.  Repair or
recalibrate time
and/or rotameter
and repeat the
sampling or ob-
tain acceptance
from a represen-
tative of the
Administrator

2.  As above
                          3.  Void the
                          test, or use an
                          alternative
                          procedure
                          acceptable to
                          a represen-
                          tative of the
                          Administrator
          (continued)
i

-------
Table 4.1  (continued)
                                                              Section No. 3-13.4
                                                              Date  July 1, 1986
                                                              Page 24
                                                                 o
 Operation
 Acceptance limits
Frequency and method
    of measurement
  Action if
requirements
are not met
Sampling
  (Method 6B
  rate constant)
1.  Sample at a con-
stant rate of between
20 and 40 ml/min
1.  Calculate sample
rate at the completion
of run
                  2.  Sample time is 24
                  hours and the accept-
                  able sample volume
                  is between 25 and 60
                  liters

                  3.  Less than 2% leak-
                  age at 500 mm (20 in.)
                        2.  Calculate sample
                        volume at end of sample
                        run
                        3.  Leak check after
                        sample run (mandatory)
1.  Repair or
recalibrate
rotameter, and
repeat run or
obtain accept-
ance from a
representative
of the
Administrator

2.  As above
                          3.  Void the
                          test, or use an
                          alternative
                          procedure
                          acceptable to
                          a represen-
                          tative of the
                          Administrator
               O
Sample Recovery
1.  Balance accurate
to within 0.1 g
                  2.  Determine mois-
                  ture collected in
                  impingers
1. Calibrate with
Class S weights
                        2.  Wipe the outside
                        of the impingers and
                        bubblers clean, and
                        weigh each to the
                        nearest 0.1 g
1. Adjust, re-
pair, or
reject

2.  Repeat run,
or use alter-
native mois-
ture determi-
nation technique
(continued)
                                                                                   O

-------
Table 4.1.   (continued)
                                                                Section No. 3.13.4
                                                                Date  July 1, 1986
                                                                Page 25
 Operation
Sample logis-
  tics (data)
  and packing
 Acceptance limits
                  3.  Recover SO,
                  sample
                  4.  Determine CO,
                  absorber weight
1.  All data are re-
corded correctly
                  2.  All equipment ex-
                  amined for damage and
                  labeled for shipment
                  3.  All sample con-
                  tainers properly
                  labeled and packaged
Frequency and method
    of measurement
                        3.  Place contents of
                        the two midget
                        impingers and the rins-
                        ings in a marked poly-
                        ethylene bottle
                        (Method 6A); place con-
                        tents of the two midget
                        impingers, the first
                        midget bubbler, and the
                        rinsings in a marked
                        polyethylene bottle
                        (Method 6B)

                        4.  Wipe clean the out-
                        side of the CO- absor-
                        ber, and weigh to the
                        nearest 0.1 g
1.  Visually check upon
completion of each run
and before packing

2.  As above
                        3-  Visually check upon
                        completion of test
  Action if
requirements
are not met
                          3. Repeat run,
                          or place con-
                          tents and rins-
                          ings directly
                          into the vol-
                          umetric flask
                          4,  Repeat run,
                          or weigh ab-
                          sorber again
1.   Complete
the data
form

2.   Redo test
if damage
occurred during
testing

3.   Correct
when possible

-------
o
o
o

-------
                                               Section No. 3.13.5
                                               Date July 1, 1986
                                               Page 1
5.0  POSTSAMPLING OPERATIONS
    Table  5.1  at the end of this section summarizes the quality
assurance activities for postsampling operations.

5.1  Apparatus Check

    A posttest check—including  a  calibration check, the clean-
ing,  and/or  the  performance of routine maintenance—should  be
made on most  of  the  sampling  apparatus.  Cleaning and mainte-
nance of the sampling  apparatus are discussed in Section 3.13.7.
Figure 5.1 should be used to record the posttest checks.

5.1.1  Metering System - The metering system has three components
that  must  be checked: dry gas  meter  thermometer(s),  dry  gas
meter, and rotameter.

    The dry gas meter thermometer should be checked by comparison
with  the ASTM mercury-in-glass thermometer at room  temperature.
If  the readings agree within  6 C  (10.8 F),  they  are  accept-
able.  When the readings are outside  this limit, the thermometer
must  be recalibrated according to Section 3.13.2 after the post-
test check of the dry gas meter.   For  calculations, the dry gas
meter  thermometer  reading (fifeld or recalibration)  that  would
give  the  higher  temperature  is  used.   That is, if the field
reading is higher, no correction of the data is necessary; if the
recalibration value is higher, the difference in the two readings
is added to the average dry gas meter temperature reading.

    The  posttest  checks of the dry gas meter and rotameter  are
similar to the  initial  calibration,  as  described  in  Section
3.13.2, but they include the following exceptions:

    1.   The metering  system •should  not  have  had  any  leaks
corrected prior to the posttest check.  ,

    2.    Three  or  more revolutions of the dry  gas  meter  are
sufficient.

    3.    Only  two  independent runs need be made.  If the post-
test dry gas meter calibration factor (Y) does not deviate by  >5
percent  from  the  initial calibration factor, the dry gas meter
volumes  obtained during the test series are acceptable.   If  it
deviates  by >5 percent, recalibrate the metering  system  as  in
Section  3.13.2  using  the   calibration   factor  (initial  and
recalibration)  that  yields the lower gas volume for  each  test
run.  The lesser calibration  factor  will  give  the  lower  gas
volume.
                            ?
    The  rotameter calibration factor (Y ) can also be determined
during  the  calibration of the dry gas meter.  If  Y   does  not

-------
                                               Section No. 3.13.5
                                               Date July 1, 1986
                                               Page 2
Meter Box Number
Dry Gas Meter (If applicable)

Pretest calibration factor (Y) =    I > 02.1
Posttest check (Y) = _ /.£>33      (+5 percent of pretest
  factor)*                           ,
Recalibration required?      yes   *  no
If yes, recalibration factor (Y) = _ (within 2 percent of
  calibration factor for each calibration run)
Lower calibration factor Y (pretest or posttest) =
  for calculations
Rotameter

Pretest calibration factor (Y ) =    /•'
Posttest check (Y ) =   /./  ( within 10 percent of pretest
  factor)        r
Recalibration recommended?       yes   s   no
If performed, recalibration factor (Y ) = _ _ ''_
Was rotameter cleaned?   _ _yes         no


Dry Gas Meter Thermometer (If applicable)
o
Was a pretest meter temperature correction used?  _ yes      no
If yes, temperature correction _ _ _
Posttest recalibration required?      yes   / no   (recalibrated
  when Y- recalibrated)
        LJ


Barometer

Was pretest field barometer reading correct?  *  yes  _ no
o
Posttest recalibration required?  	yes   __j/_no (recalibrated
  when YL recalibrated)


Balance*

Was the balance calibration acceptable?     tX^yes 	 no
   (;+ 0.05 g checked against Class S weights)
If no, the balance should be repaired or replaced prior to
  weighing field samples.
* Most significant items/parameters to be checked.

             Figure 5.1.   Posttest sampling checks.
                                                                     O

-------
                                               Section No. 3.13.5
                                               Date July 1, 1986
                                               Page 3

deviate by >10 percent from the  initial  calibration factor,  the
rotameter operation is acceptable.  If Y  changes by >10 percent,
the rotameter should be cleaned and recalibrated.  No corrections
need be made for any calculations.

5.1.2  Barometer - The field barometer readings are acceptable if
they agree within 5 mm (0.2 in.) Hg when compared  with  those of
the  mercury-in-glass  barometer.   When the  comparison  is  not
within this range, the lesser  calibration  value  should be used
for the calculations.  If the field barometer  reads  lower  than
the mercury-in-glass  barometer,  the  field data are acceptable;
but if the mercury-in-glass barometer  gives  the  lower reading,
the barometric  value  adjusted  for  the  difference  in the two
readings should be used in the calculation.

5.1.3   Balance  -  The  balance should have been  calibrated  as
described in Subsection 4.3.1.

5.2  Analysis (Laboratory)

    The purpose of Method 6B  is  to  provide  an  average  daily
emission rate for each 24-hour sample.  These emission  rates are
used   for  decision  making  and  determining  rolling   average
compliance status.  As a result, the values must be determined in
a timely  manner.   It  is  therefore  assumed that the Method 6B
analyses  are  performed  either  on-site  or within a reasonably
short distance from the  site.  Both the analytical equipment and
techniques lend themselves,  when  performed  in  a clean area by
skilled technicians, to providing the necessary accuracy.  A base
laboratory is not required.

    Calibrations  and  standardizations  are of the utmost, impor-
tance to a precise and accurate analysis.  The analysis  is based
on the insolubility of barium sulfate (BaS04)  and  on  the  for-
mation of the colored complex between excess barium ions  and the
thorin  indicator,  l-(o-arsonophenylazo)-2-naphthol-3,  6-disul-
fonic  acid, disodium salt.  Aliquots from the impinger  solution
are analyzed by titration with  barium  perchlorate  to  the pink
endpoint.  The barium ions react preferentially with sulfate ions
in   solution   to  form  a  highly  insoluble   barium   sulfate
precipitate.  When the barium has reacted with all of the sulfate
ions, the excess barium then reacts with the thorin  indicator to
form a metallic salt of the indicator and  to give a color change
as shown in Equation 5-1.


Ba++ + SOA~ + thorin(x++) -> BaSO, + thorin(Ba  )    Equation 5-1
                (yellow)                (pink)

    Upon  completion of each step of the  standardization  or  of
each  sample  analysis,  the data should be entered on the proper

-------
                                               Section No.  3.13.5
                                               Date July 1,  1986
                                               Page 4

data form.  At the conclusion of  the  sample  analysis, the data
form should be reviewed and signed by the laboratory  person with
direct responsibility for the sample.

5.2.1   Reagents  (Standardization  and Analysis) - The following
reagents are required for the analysis of the samples:

    Water  -  Deionized  distilled  water that conforms  to  ASTM
specification D1193-74,  Type 3 is required.   At the option of the
analyst,  the  KMnO. test for oxidizable organic  matter  may  be
omitted  when  high concentrations  of  organic  matter  are  not
expected.   Note;   The water must meet the  ASTM  specifications
since sulfate ions and many other  anions  present  in  distilled
water  are  not identified in the normal standardization  of  the
acid  by  NaOH titration, which measures the hydrogen ion concen-
tration  rather than the sulfate ion concentration.   This  added
sulfate concentration will result in an erroneous standardization
of the barium  perchlorate  titration,  which  directly  measures
sulfate  ion concentration and not hydrogen ion concentration.  A
check on the acceptability of the water is detailed in Subsection
5.13.4.

    Isopropanol  -  100  percent,  ACS  reagent  grade is needed.
Check  for  peroxide impurities as described  in  Section  3.13.1
(Method 6A).

    Thorin indicator  -  Dissolve  0.20  +0.002 g of l-(o-arsono-
phenylazo)-2-naphthol-3,6-disulfonic  acid, disodium salt, or the
equivalent, in 100  ml  of water.  Measure the distilled water in
the 100-ml graduated cylinder (Class A).

    Sulfuric  acid  standard,  0.0100N - Either purchase manufac-
turer-guaranteed  or  standardize the H2S04  to  +0.002N  against
0.0100N NaOH that has been standardized  against  potassium  acid
phthalate  (primary  standard  grade)  as described in Subsection
5.13.3.  The 0.01N H2S04 may be prepared in the following manner:

     a. Prepare 0.5N H2S04 by adding  approximately  1500  ml  of
        water to a 2-liter volumetric flask.

     b. Cautiously  add  28  ml of concentrated sulfuric acid and
        mix.

     c. Cool if necessary.

     d. Dilute to 2-liters with water.

     e. Prepare 0.01N H-SO. by first adding approximately 800  ml
        of distilled water to a 1-liter volumetric flask and then
        adding 20.0 ml of the 0.5N H0SO..
                                    24
     f. Dilute to 1-liter with water and mix thoroughly.
o
o

-------
                                               Section No. 3.13.5
                                               Date July 1, 1986
                                               Page 5

    Barium  perchlorate  solution  0.0100N - Dissolve 1.95  g  of
barium  perchlorate trihydrate  (Ba(C104)2.3H2O)  in  200  ml  of
water, and dilute to 1-liter  with  isopropanol.   Alternatively,
1.22  g  of  barium  chloride  dihydrate (BaCl2.2H2O) may be used
instead  of  the  perchlorate.   Standardize,  as  in  Subsection
5.13.4, with  0.0100N  H2SO4.   Note;  Protect the 0.0100N barium
perchlorate solution from evaporation at all times by keeping the
bottle capped between uses.

    Note;   It  is  recommended that 0.1N sulfuric acid  be  pur-
chased.  Pipette 10.0 ml of sulfuric acid  (0.1N)  into  a 100-ml-
volumetric  flask  and dilute to volume with water that has  been
determined  to  be acceptable as detailed in  Subsection  5.13.4.
When  the  0.0100N  sulfuric acid is  prepared  in  this  manner,
procedures in Subsections 5.13.2. and 5.13.3 may be omitted since
the standardization  of barium perchlorate will be validated with
the control sample.

5.2.2  Standardization of Sodium Hydroxide - To standardize NaOH,
proceed as follows:

    1.   Purchase  a  50 percent w/w NaOH solution.  Dilute 10 ml
to 1-liter with water.  Dilute 52.4 ml of the diluted solution to
1-liter with water.

    2.   Dry the primary standard grade potassium acid  phthalate
for 1 to 2 hours at 110 C (230 F), and cool in desiccator.

    3.   Weigh to the nearest 0.1 mg, three 40-mg portions of the
phthalate.   Dissolve  each portion in 100 ml of  freshly  boiled
water in a 250-ml Erlenmeyer flask.

    4.   Add two drops of phenolphthalein  indicator, and titrate
the phthalate solutions with the NaOH solution.   Observe  titra-
tions  against a white background to facilitate detection of  the
pink endpoint.   The  endpoint is the first faint pink color that
persists for at least 30 seconds.

    5.   Compare the endpoint  colors of the other two titrations
against the first.

    6.   Titrate a blank of 100  ml  of  freshly boiled distilled
water using the same technique as in step 4.  (The  normality  is
the average of  the  three  values calculated using the following
equation.)


              _ 	mg KHP	     Equation 5-2
              ~
                (ml Titrant - ml Blank) x (204.23)

-------
                                               Section No. 3.13.5
                                               Date July 1, 1986
                                               Page 6

 where                      —-

        NN QH = calculated normality of sodium hydroxide,

       mg KHP = weight of the phthalate, mg,

   ml Titrant = volume of sodium hydroxide titrant, and

     ml Blank = volume of sodium hydroxide titrant for blank (ml).

    The  chemical reaction for this standardization  is  shown  in
Equation 5-3.  The  sodium  hydroxide  is  added  to the potassium
hydrogen phthalate and  colorless  phenolphthalein  solution until
there  is  an  excess  of diluted hydroxyl ions which  causes  the
phenolphthalein solution to change to a pink color.

                                                     Equation 5-3

NaOH + KHP + phenolphthalein -> KNaP + HOH + phenolphthalein
               (colorless)                         (pink)

5.2.3  Standardization of Sulfuric Acid - To standardize sulfuric
acid, proceed as follows:

    1.    Pipette  25  ml of the H2S04 into each of three  250-ml
Erlenmeyer flasks.

    2.   Add 25 ml of water to each.

    3.   Add two drops  of phenolphthalein indicator, and titrate
with  the  standardized  NaOH  solution  to  a  persistent   pink
endpoint, using a white background.

    4.   Titrate a blank of 25 ml of  water, using the same tech-
nique as step 3.  The normality will be the average  of  the three
independent values calculated using the following  equation:


       _ (ml NaOHacid - ml NaOHblank) X NNaOH       Equation 5-4
 w cr\  ~~                  o ^
 n**&\J *                    £*
-------
                                               Section No. 3.13.5
                                               Date July 1, 1986
                                               Page 7

    1.   Pipette 25 ml of sulfuric acid standard  (0.0100N)  into
each of three 250-ml Erlenmeyer flasks.

    2.   Add 100 ml of reagent grade isopropanol  and two to four
drops of thorin indicator, and titrate to  a  pink endpoint using
0.0100  N  barium perchlorate.   Perform  all  thorin  titrations
against a white background to facilitate  the  detection  of  the
pink endpoint color.

    3.   Prepare a blank by adding 100 ml of isopropanol to 25 ml
of water.  If a blank requires >0.5 ml of  titrant,   the  analyst
should determine the source of contamination.  If  the  distilled
water contains high concentrations of sulfate of other polyvalent
anions,  then all reagents made with the water will  have  to  be
remade using distilled water that is acceptable.

    4.   Use the endpoint of the blank  or  the  endpoint  of the
first  titration  as  a  visual  comparator  for  the  succeeding
titrations.

    5.   Record data on analytical  data  form,  Figure 5.2.  The
normality of the barium  perchlorate  will  be the average of the
three independent values calculated using Equation 5-5.

                       NH SQ  x  25

        NBa(C104)2 =  	     Equation 5-5
                      (ml Ba(ClO4)2 - ml Blank)

where

  N_ ,_-o «  = calculated normality of barium perchlorate,
         4 2
      NIT or>  = normality of standardized sulfuric acid,
       H2S04
 ml Ba(Cl04)2 = volume of barium perchlorate titrant, ml, and

    ml Blank = volume of barium perchlorate titrant for blank, ml.

The  chemical  reaction  for  this  standardization was shown  in
Equation  5-1.   The  standardized  barium perchlorate should  be
protected from evaporation of the isopropanol at all times.

Note:    It is suggested that the  analyst  unfamiliar  with  this
titration carry out titrations  on  aliquots  at low, medium, and
high concentrations in the following manner:

   1.  Pipette 2.0-, 10.0-, and 20.0-ml  aliquots of 0.0100N H2SO4
into three 250-ml Erlenmeyer flasks.

   2.  Dilute to 25 ml with distilled water.

-------
Plant   /fc/Kl   fbv>&r  P)*>*r&      Date 	
Sample location  &/£r /Vy. 3	  Analyst
Volume and normality of barium perchlorate

Standardization blank 0.0 ml (< 0.5 ml)
                                                               Section No. 3-13.5
                                                               Date July 1, 1986
                                                               Page 8
                                                                      N
I 2.4. TZ  ml j
2 2.4-. SO   ml t	
3  Zfr.50  ml Q.QIOZO N
              0-0102. N, avg
                                                                                o
Sample
number
1
2
3
4
5
6
Field
Blank
Sample
identification
number
AP-I






Total
sample
volume
 •
ml
100





N/A
Sample
aliquot
volume

  Volume for the blank must be the same as that of the sample aliquot.
b 1st titration
  2nd titration
  Signature of analyst
                = 0.99 to 1.01 or  1st titration - 2nd titration  £0.2 ml.

                           KoH K:
  Signature of reviewer or supervisor   \&fl/)l'//# ^  {£L/($\ (L>
                                                     J
                      Figure 5-2.  Sulfur dioxide analytical data form.
                                                                                 O

-------
                                               Section No. 3.13.5
                                               Date July 1, 1986
                                               Page 9

    3.  Add a 100-ml volume of 100 percent isopropanol and two to
four drops of thorin indicator to each.

    4.  Titrate with  barium  perchlorate to become familiar with
the endpoint.

5.2.5  Control Samples - The accuracy and precision of the sample
analysis should be checked.  The accuracy of the analytical tech-
nique is determined by control samples.  The precision is checked
by duplicate analyses of both the control  and the field samples.
Acceptable accuracy and precision should  be  demonstrated on the
analysis of the control sample prior to the analysis of the field
samples.

    The control sample  should  be  prepared  and analyzed in the
following manner:

   1. Dry the primary standard grade ammonium sulfate ((NH4)_S04)
for 1 to 2 hours at 110 C (230 F), and cool in a desiccator.

   2. Weigh to the  nearest  0.5 mg, 1.3214 g of primary standard
grade ammonium sulfate.

   3. Dissolve the reagent in about 1800 ml of.distilled water in
a 2-liter volumetric flask.

   4. Dilute  to  the  2-liter  mark  with  distilled water.  The
resulting solution is 0.0100N ammonium sulfate.

   5. Enter all data on the form shown in Figure 5.3.

   6. Pipette 25 ml of the  control  sample  into  each  of three
250-ml Erlenmeyer flasks, and pipette a 25-ml blank of  distilled
water into a fourth 250-ml Erlenmeyer flask.  Note;  Each control
sample will contain 16.5 mg of ammonium sulfate.

   7. Add 100 ml of reagent grade  isopropanol  to each flask and
then two to four drops of thorin indicator.

   8. Initially, titrate the blank to a faint pink endpoint using
the  standardized  barium  perchlorate.   The  blank must contain
< 0.5 ml of titrant, or the water is unacceptable for use in this
method.

   9. Titrate two of the control  samples  with  the standardized
barium  perchlorate  to  a  faint  pink  endpoint using the blank
endpoint  as  a guide.  The endpoint  is  the  first  faint  pink
endpoint  that  persists for at least 30 seconds.  All titrations
should be done against a white background.

-------
                                               Section No. 3.13.5
                                               Date July 1, 1986
                                               Page 10
                                                                   o
Plant
Analyst   /£«»•£;   tirqn
                                   Date analyzed

                                   NT
                                    'Ba(Cl04)2
    Weight of ammonium sulfate is 1.3214 g?

    Dissolved in 2 L of distilled water?
                                                I
                                               yes,
    Titration of blank   0-0  ml Ba(C104)2 (must be <0.5 ml)
Control
sample
number
/
Time of
analysis,
24 h
0350
Titrant volume,3 ml
1st
2.S.O
2nd
2.^.0
3rd

Avg
2S.O
(
                                                                   O
      Two titrant volumes must agree within 0.2 ml.

(ml Ba(C10.)0 - ml Blank) x N_ , ~, n *    ot- „.    0
          42                Ba(ClO^)2 = 25 ml x  0
                                       (control) (control
                                        sample)   sample)
ml -
mi)
                          O.
                                N =
(must agree within 5%, i.e., 0.238 to 0.262)

Does value agree?  *   yes  	no

                                       Signature of analyst

                                       Signature of reviewer

        Figure 5.3.   Control sample analytical data form.
                                                                  O

-------
                                               Section No. 3.13.5
                                               Date July 1, 1986
                                               Page 11

10.   If the titrant  volumes  from the first two control samples
agree within 0.2 ml, the average of the two values can be used to
complete the calculations shown in Figure 5.3.  If not within 0.2
ml, titrate the third control sample.   If  the  titration volume
agrees within 0.2 ml of either of the first two  samples, use the
two  titrant  volumes  that  are  consistent  for  the  remaining
calculations.  If this criterion cannot be met with the first set
of control samples,  follow the same procedure on a second set of
two control samples.

   11.    If  the  criterion  cannot be met for the second set of
control  samples,  the  analyst  should have the analytical tech-
niques observed by a  person  knowledgeable in chemical analysis,
or should have all reagents checked.

   12.   After consistent titrant volumes are obtained, calculate
the analytical accuracy as shown  in Figure 5.3.  If the measured
value is within  5 percent of the stated value, the technique and
standard reactions  are  acceptable, and the field samples may be
analyzed.  When the 5 percent accuracy  cannot be met, the barium
perchlorate must be  restandardized or the control sample must be
checked  until  the  accuracy  criterion  of  the  control sample
analysis can be obtained.

   13.    The  recommended  frequency  for  analysis  of  control
samples is the following:

   a.  Analyze two control samples each  analysis day immediately
       prior to analysis of the actual collected source samples.

   b.  Analyze  two  control  samples  after  the  last collected
       source sample is analyzed each analysis day.

   14.  Enter results  from the control sample analyses on Figure
5.3,  and  submit Figure 5.3  with  the  source  test  report  as
documentation of the quality of the source test analysis.

5.2.6  Sample  Analysis  -  Check the level of liquid in the con-
tainer to determine whether  any sample was lost during shipment,
and note this on the data form, Figure  4.3.   Figure  5.4 can be
used to check analytical procedures.  If a noticeable  amount  of
leakage has  occurred,   follow  the  alternative method described
below.  Approval should have  been  requested prior to testing in
case  of  subsequent  leakage.    The  alternative  method  is  as
follows:

    1.  Mark the new level of the sample.

    2.  Transfer the sample to a 100-ml volumetric (vsoln) flask,
and dilute to exactly 100 ml with deionized distilled wa?er.

-------
                                               Section No. 3.13.5
                                               Date July  1, 1986    /—x
                                               Page 12              (   }
Reagents
Normality of sulfuric acid standard*     0- 010$ N	
Date purchased    /&//0/6f    Date standardized /£>//£/gfT
Normality of barium perchlorate titrant*    0, ()6ef(t> 14  A/
Date standardized 	?//£»/£ 5"!	
Normality of control sample*	Q. 6/OOd	
Date prepared 	/^//& / &£~	:	
Volume of burette     ^OrH-O.     Graduations   &•/
Sample Preparation
Has liquid level noticeably changed?*
Original volume 	  Corrected volume
Samples diluted to 100 ml?* 	
Analysis                              '
(Sulfur dioxide)
Volume of aliquot analyzed* 	
Do replicate titrant volumes agree within 1% or 0.2 ml? uc^>         /"""N
Number and normality of control samples analyzed 2.$) Q. lOQfiJ         \)
Are replicate control samples within 0.2 ml? 	
Is accuracy of control sample analysis +5%7* 	
Is the relative error of audit sample(s) within acceptable
  limits?* 	U<£~5	
                 7
(Moisture and carbon dioxide)
Balance calibrated with Class S weights to within 0.05 g?*
               _
Initial weignt of each impinger to nearest 0.1 g*
Final weight of each impinger to nearest 0.1 g*
                                                _
Initial weight of CO., absorber to nearest 0.1 g*
Final weight of CO.- absorber to nearest 0.1 g*
                  2

All data recorded? _ r _  Reviewed by
*Most significant items/parameters to be checked.

                Figure 5.4.  Posttest operations.
o
                                                    ([

-------
                                                Section No. 3.13.5
                                                Date  July  1,  1986
                                                Page  13

     3.    Put  water in  the  sample  storage container to the initial
 sample  mark,  and measure the  initial  sample volume (V     ).
                                                     som .

     4.    Put  water in  the  sample  storage container to the mark of
 the  transferred  sample, and measure the final volume (V      ).
                                                       SO J-ii *«
     5.    If vsoln   is  < Vsoln  ' correct "fc*16 sample volume  ,..     .
 by using  Equationf5-6,       i                              soln
              Vsoln   - Vsoln       1                 Equation 5-6


where
    V     ' = sample volume to be used for the calculations, ml,

    V   .  = total volume of solution in which the sulfur diox-

            ide is contained, ml,

   Vsoln  = initial sample volume placed in storage container,
            ml , and

          = final sample volume removed from storage container,
        .C     .
        f   ml .

    6.  Both  the corrected and uncorrected values should be  sub-
mitted  in the test report to the Agency.

Proceed with  the analysis as follows:

    1.   Transfer the contents of the sample bottle to  a  100-ml
volumetric  flask  (V  1 ), and dilute to the mark with deionized
distilled water.     SOJ-n

    2.   Pipette  a  20-ml  aliquot (V ) of this solution into  a
250-ml  Erlenmeyer flask,  and  add  80a ml of 100 percent isopro-
panol .

    3.  Add two to four drops of thorin indicator, and titrate to
an orange-pink endpoint using standardized  0.0100N  barium  per-
chlorate.   Record the  volume  of  barium  perchlorate  used  in
titrating  the  sample  (V4-)«   If more than 100 ml of titrant is
required,  then a smaller sample aliquot should  be  used  (i.e.,
1.0 ml).   If  less than 5 ml of titrant is required, the analyst
may prepare the titrant with a normality of 0.0010 when a greater
precision is desired.

    4.  Repeat the above analysis on a new  aliquot from the same
sample.  Replicate  titrant  volumes  must be within 1 percent or
0.2 ml, whichever is greater.  If the titrant volumes do not meet
this criterion,  repeat  analyses  on  new  aliquots of the sample
until two consecutive titrations agree  within  1  percent or 0.2
ml, whichever is greater, or until sample is spent.

-------
                                               Section No. 3.13.5
                                               Date July 1, 1986
                                               Page 14

    5.   Record all data on the data form, Figure  5.2.   Average
the consistent  titrant  volumes,  and  use  them as V, in subse-
quent calculations.  All analytical data must then be reviewed by
a  person  familiar with procedures, and this  review  should  be
noted on the data form,  Figure  5.2.  Note:   Protect the 0.0010N
barium perchlorate solution from evaporation at all times.

    Warning;   Contamination  of  the  sample  with  Ascarite  or
Drierite  will  cause  bias.  The analyst should take precautions
when  handling  Ascarite or Drierite  and  the  field  sample  or
absorbing  solution so as not to introduce these  materials  into
the sample or absorbing solution.

    Note;   References 2 and 3 contain additional information  on
improved temperature stability and  application  of  Method  6 to
high sulfur dioxide concentration.
                                                                    O
                                                                    o

-------
                                                              Section No. 3.13-5
                                                              Date July 1, 1986
                                                              Page 15
            Table  5.1.  ACTIVITY MATRIX FOR POSTSAMPLING OPERATIONS
 Activity
  Acceptance  limits
Frequency and method
    of measurement
  Action if
requirements
are not met
 Sampling
 Apparatus

 Dry gas meter
Within  5% of pretest
calibration factor
Make two independent
runs after each field
test
Recalibrate and
use calibration
factor that gives
lower sample
volume
Rate meter
Within 10* of desired
flow rate  (recommended)
Make two independent
runs during the check
of the rate meter
Clean and
recalibrate
Meter thermom-
eter
Within 6°C  (10.8°F)
at ambient  temperature
Compare with ASTM
mercury-in-glass
thermometer after each
field test
Recalibrate and
and use higher
temperature value
for calculations
Barometer
Within 5.0 mm
(0.2 in.) Hg at
ambient pressure
Compare with mercury-
in-glass barometer
after each field test
Recalibrate and
use lower baro-
metric value for
calculations
Balance
Within 0.05 g
Compare against Class S
weights
Adjust, re-
pair, or re-
place
Analysis

Reagents
Prepare according to
requirements detailed
in Subsection 5-2
Prepare and/or stan-
dardize within 24 h of
sample analysis
Prepare new solu-
tions and/or re-
standardize
Control sample
Titrants differ by
£0.2 ml; analytical
results within 5% of
stated value
Before and after
analysis of field
samples
Prepare new solu-
tions and/or
restandardize
Sample
analysis
Titrant volumes differ
by <1% or <0.2 ml,
whichever is greater
Titrate until two or
more consecutive ali-
quots agree within 1%
or 0.2 ml, whichever is
greater, review all
analytical data
Void sample if
a set of two
titrations do
not meet
criterion

-------
o
o
o

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                                               Section No. 3.13.6
                                               Date July 1, 1986
                                               Page 1
6.0  CALCULATIONS
    Calculation errors due to procedural or mathematical mistakes
can be a part of total system error.   Therefore,  it  is  recom-
mended  that each set of calculations be repeated or spotchecked,
preferably by a team  member other than the one who performed the
original calculations.  If  a  difference  greater  than  typical
round-off  error  is detected, the calculations should be checked
step-by-step until the source of error is found and corrected.  A
computer program is advantageous  in reducing calculation errors.
If  a standardized computer program is used,  the  original  data
entry should be included  in  the  printout  to  be  checked;  if
differences are observed,  a  new  computer  run  should be made.
Table  6.1 at the end of  this  section  summarizes  the  quality
assurance activities for calculations.

    Calculations should be carried  out  to  at  least  one extra
decimal  figure  beyond that of the acquired data and  should  be
rounded off after final calculation to two significant digits for
each  run  or  sample.   All  rounding  off  of numbers should be
performed  in  accordance  with the ASTM 380-76 procedures.   All
calculations should then be recorded on  a  calculation form such
as the ones in Figures 6.2A and 6.2B, at the end of this section.

6.1   Nomenclature

    The following nomenclature is used in the calculations:
    'CO,
    i  *
    'SO,
     w
    sso.
    m
     wi
    m
     wf
    m
    m
    m

    N
ai
af
SO,
= concentration of CX>2, dry basis, percent,
= concentration of sulfur dioxide, dry basis

  corrected to standard conditions, mg/dscm (Ib/dscf),

= concentration of moisture, percent,

= emission rate of S02, lb SO2/million Btu (ng/J),

= volume of C02 liberated per million Btu of

  heat release, dscm (dscf),

= initial mass of impingers, bubblers, and moisture

  absorber, g,

= final mass of impingers, bubblers, and moisture

  absorber, g,

= initial mass of C02 absorber, g,

= final mass of C02 absorber, g,

= mass of S02 collected, mg,
= normality of barium perchlorate titrant, milliequi-

  valents/ml,

-------
                                               Section No. 3.13.6
                                               Date July 1, 1986
                                               Page 2               /•— N
    P.    = barometeric pressure at the exit orifice of              ^^
           the dry gas meter, mm Hg (in. Hg),
                                 TP- ""^
    P ,  . = standard absolute pressure, 760 mm Hg (29.92 in. Hg),
    T  •  = average dry gas meter absolute temperature, °K  (°R),
    Tstd = s'tandard absolute temperature, 293°K (528°R),
    V_   = volume of sample aliquot titrated, ml,
     3
VCO (std)= standard equivalent volume of C02 collected,
           dry basis, m ,
    V    = dry gas volume measured by dry gas meter, dcm (dcf),
 V ,  ..» = dry gas volume measured by dry gas meter, corrected to
           standard conditions, dscm (dscf),
   Vsoln = total volume of solution in which the sulfur
           dioxide sample is contained, 100 ml,
    V.   = volume of barium perchiibfate titrant used for the
           sample (average of replicate titrations), ml,
    V. .   = volume of barium perchlorate titrant used for the
           blank, ml,                                              /""N
 V ..... = volume of water at standard conditions,  dscm (dscf),    > — s
    Y    = dry gas meter calibration factor, and
  32.03  = equivalent weight of sulfur dioxide.

6.2  Calculations for Concentration
    The following formulas for calculating  the  concentration of
sulfur dioxide, using metric units, are to be used  along with the
example calculation forms shown in Figures 6.1, 6. 2A,  and  6.2B.
6.2.1  CC^ Volume Collected, Corrected to Standard  Conditions -

        VC00(std) = 5'467 x 10~4 (maf - mai)         Equation 6-1
6.2.2  Moisture Volume Collected,' Corrected to Standard Conditions -
        Vr,/=+-^ = 1-336 x 10~° (m _ - m  . )           Equation 6-2
         W^ S^U /                  Wi    WJL
                                                                   o

-------
6.2.3  S02 Concentration
              = 32'03
                                   / Vsoln \
                      (Vt - Vtb) N \  Va  /

                      Vm(std) + VC02(std)
                                               Section No. 3.13.6
                                               Date July  1,  1986
                                               Page 3
                                                     Equation  6-3
6.2.4  CO0 Concentration -
         £* """ ' -----    .-....._--
                      'C02(std)
       CC02    Vm(std)  + VC02(std)


6.2.5  Moisture Concentration -
                                    x 100
                                                     Equation 6-4
            Cw = V
                         'H20(std)
                  m(std) + VH20(std) + VC02(std)
6.3  Emission Rate Calculations
                                                     Equation 6-5
    If the only  emission  measurement  desired  is  in  terms of
emission  rate  of SO« (ng/J), an abbreviated  procedure  may  be
used.  The  differences  between  Method  6A  and the abbreviated
procedure are described in Subsection 4.3.
6.3.1
           Mass Collected -
        mso2 = 32'03 ^vt -
where
        m.
             = mass of S00 collected, mg.
                                                     Equation  6-6
6.3.2  Sulfur Dioxide Emission Rate -
where
                                 mso
        Ec-  = F  (1.829 x 109)-	^-——x
         S02    c               (maf ' mai)
                                                     Equation  6-7
        Ec-  = emission rate of S00, ng/J, and
         oU/,                      ft
                                                     3
        F    = carbon F factor for the fuel burned, m /J,
         c     from Method 19.

-------
                                               Section No. 3.13.6
                                               Date July 1, 1986
                                               Page 4
                METER VOLUME (metric to English)

    V  =   33.^6 liter
     m   — — —   — —    •            ,,                       Q
    V  = Vm (in liters) x 0.03531 ft^/liter = l_ . _/ 8 7_ 2^ ftJ


                METER TEMPERATURE (metric to English)

     m   — —   —
    tm = [tm (°C) x 1.8] + 32 = _ J2- . 3 °F

    T  = t  (°F) + 460 = ^"3 2_ . 3°R


                BAROMETRIC PRESSURE (metric to English)

    pbar = 7f 2 . mm Hg

    Pbar = Pbar ^mm Hg^ x °-03937 ln- H9/mm Hg = Z ^.  - 8 O^ in. Hg
            METER VOLUME (English to metric)

V  = / .  / 6  f 7-  f t3
 rn   -' _   T - •  _ _*_  - __

          t3) x 0.02832 m3/ft3 = .O^S_ &&_ m3                    (^\



            METER TEMPERATURE (English to metric)
     m    m
    tm = [tm (°F) - 32] x 5/9 = 2-_^. 4 °C

    T  = t  (°C) + 273 = 2-f .T.   °K
                BAROMETRIC PRESSURE (English to metric)

    pbar = ^i ' £2- in' Hg
    Pbar = Pbar (in* Hg) x 25*4 "^ Hg/±n- Hg = 1^2  •
Figure 6.1.  Method 6A and 6B calculation form  (conversion  factors).
                                                                     o

-------
                                             Section No.  3.13.6
                                             Date July 1,  1986
                                             Page 5
              STANDARD METER VOLUME (English units)
V
 m
           '  1 & ! 2: ft,  Y = / .  0


         21 -  £ 0_ in.  Hg, Tm = 53 £ .  3 °R
  V (std) = 17.64 VY
   m
                   m
                     bar
                           m
= _/ .  2 5" 7 6 dscf
            CO,, VOLUME COLLECTED, STANDARD CONDITIONS
              £
                           (English units)

           maf = 3 £ 8 .  3 g, m   = 3 £ £ .  /_ g
    (std) - 0.01930 (m . - in. ) = 0 •  I £~G3 dscf
                      an    ai    —   — — — —
                                                     Equation 6-1
            C02 CONCENTRATION (percent by volume)
           V
            CO
 'CO,
              2(std)
                            x 100 = J{_  . )_~?_
       Vm(std)
                     V co (std)
                         Q. ' £
        SO2 CONCENTRATION (English units)


        30 ml, Vtb * 0 . Q_b_ml, N = £  . 0 £ 2.2  (g-eq)/ml

        Q . 0 ml. V  = 2-0 . O ml
'SO,
     = 7.061 x IP"5 (Vt - Vtb)N/Vsoln\   £ . £ 8 ^ £ x 10~4 Ib/dscf
             std> + Vco2(std)
                           \ v
                                                     Equation 6-3
Figure 6.2A.  Method 6A and 6B calculation form (English units)

-------
                                             Section No. 3.13.6
                                             Date July 1, 1986
                                             Page 6
      m
       wf
           MOISTURE CONCENTRATION (percent)

                          - 2rl± ' L 9
                                                                     o
  Vw(std) = °-04707 (mwf ~ mwi) =  ' ^ ^ 2£ dscf     Equation 6-2


  c    =  __ VH20(std) _ x 100  = _ 6  • 8_ /_ %

   H2°    Vm(std) + VH00(std) + VC09(std)
                      £*            jL
                                                     Equation  6-5
              EMISSION RATE OF SO2  (English units)

                      (using meter  volumes)


FC = _/0 /_0_ scf of C02/million Btu

E_n  = C__  F    10° = 0  . Q (f £ lb S00/million Btu
 oU—    oU^  C  —      —   — — —      Z
                °                   -• -
                   (not using meter sample volume)
mS°2
= L & LO. scf of C02/million Btu                                  (  J


   = 32.03 (Vt - Vtb)N /Vsoln\= _ L & • 44 m9 of S02 collected
                             a   '
                                                     Equation  6-6
                      ^
Ecn  = F^ (1.141 x 10~  )   m__  =    ^ . 465T lb S00/million Btu
 ovJ*     C               ^   "jj o _    —   — — —      ^
                        (m
                      af   maiJ
                                                  Equation 6-7
                  SO0 CONCENTRATION  ( ppm )
C    (ppm) = CS0  db/dscf) =    / 7 Z  . 6 ppm
                              ----   ~
                2
 b°2                    -7
              1.663 x 10  X
                  Figure 6.2A.   (continued)
                                                                 O

-------
                                                Section No. 3.13.6
                                                Date July 1, 1986
                                                Page 7
                STANDARD METER VOLUME  (metric units)

                        (using meter volumes)
   vm  =    3 2> •  <£ # liter x 0.001  =  O . Q ?> 3 (*£> m
    lit   ^™"   ™~   ^~ ™"*                  ^™  ™^ ™"~~ ^™~ *~~ *^
 m


Y  = 1 - __? t L  pbar = 2 _f Z • "^ «9' Tra _£rf C" • t °K


Vm(std) =  0.3858 VmY Pbar » . 03 _f _£_£ dscm

                       Tm


           C02 VOLUME COLLECTED, STANDARD CONDITIONS

                        (metric units)
  af ~" -?i_.__ *  il 5» '   ai ~ — — — * —

                        —4
 Vrn (std)  = 5.467 x 10  (m - - m  .) =  .  0&4-4-& dscm
  (_.u2                       ar    ai       _____ j_ _
                                                      Equation 6-1


              C02 CONCENTRATION (percent by  volume)


 c            vco_5.
-------
                                           Section No. 3.13.6
                                           Date July 1, 1986
                                           Page 8

            MOISTURE CONCENTRATION (percent)


mwf = ££ 4. ' 2 9' mwi = Ml • J 9


Vm(std) " 1'336 x 10"3 (mwf - mwi> " • -?* 2-2t dscm
                                                 Equation 6-2
                                                                   o
   cu ft =   _ H,Q _ : _  x 100 =
     9U      V       + V         4-V
     z       vm(std)   vH20(std)   vCO2(std)
                                                    Equation 6-5
               EMISSION RATE OF S02 (metric units)
                      (using meter volumes)


   F  = 0 . £ & ^ x 10~  dscm of C02/J


   Eso2 « Cso2 Fc -^-- -1 $$ • 2 ng/J                            O
                   Cco2


                        (not using meter volumes)


 ?c = P • ^ ^ 4 x 10~  dscm of C02/J


n»0ft  » 32.03 (V. - V.. ) N/Vsoln\°    /& . O Z. mg of S00 collected
 so2           t:    to   1  y—|  — -t- —   — —         ^
                      /vsoln\'
                      \  Vn  /

                                                  Equation  6-6
ESQ  = Fc (1.829 x 109)   mSQ 	=__/!£• 3 ng/J

   2                         2
                                                     Equation  6-7
                    Figure 6.2B. (continued)                       ^^^

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                                                                Section No.  3.13.6
                                                                Date July 1, 1986
                                                                Page 9
                Table 6.1.  ACTIVITY MATRIX FOR CALCULATION CHECKS
Characteristics
Analysis data
   form
Calculations
  Acceptance limits
All data and calcula-
tions are shown
Difference between
check and original
calculations should
not exceed round-off
error
Frequency and method
    of measurement
Visually check
Repeat all calculations
starting with raw data
for hand calculations;
check all raw data in-
put for computer calcu-
lations; hand calculate
one sample per test
  Action if
requirements
are not met
Complete the
missing data
values
Indicate errors
on sulfur dioxide
calculation form.
Fig. 6.1A or 6.IB

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o
o
o

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                                               Section No. 3.13.7
                                               Date July 1, 1986
                                               Page 1
7.0  MAINTENANCE
    The normal  use  of emission-testing equipment subjects it to
corrosive  gases,  extremes in temperature, vibration, and shock.
Keeping  the  equipment  in good operating order over an extended
period of time requires  knowledge of the equipment and a program
of routine maintenance which is performed quarterly or after 2830
liters  (100  ft )  of  operation,  whichever  comes  first.   In
addition to the quarterly maintenance, a yearly  cleaning  of the
entire meter box is recommended.  Maintenance procedures  for the
various components are summarized in Table 7.1 at the end of  the
section.  The following procedures  are  not  required,  but  are
recommended to increase the reliability of the equipment.

7.1  Pump

    In the present commercial sampling  train,  several  types of
pumps are used; the most common  are  the  fiber  vane  pump with
in-line oiler and the diaphragm pump.  The  fiber  vane  pump re-
quires a periodic check of the oiler jar.  Its contents should be
translucent; the oil should  be changed if it is not translucent.
Use the oil specified by the manufacturer.  If none is specified,
use SAE-10 nondetergent oil.  Whenever the fiber vane pump starts
to run erratically or during  the  yearly  disassembly,  the head
should be removed and the fiber vanes changed.  Erratic operation
of the diaphragm pump is normally due to either a  bad  diaphragm
(causing leakage) or to malfunctions of the valves,   which should
be cleaned annually by complete disassembly.

7.2  Dry Gas Meter

    The dry gas meter should be checked for  excess oil or corro-
sion of the components by removing the top plate every  3 months.
The  meter should be disassembled and all components cleaned  and
checked whenever the rotation of the dials is  erratic,  whenever
the meter will not calibrate properly over the required flow rate
range, and during the yearly maintenance.

7.3  Rotameter

    The rotameter should be disassembled and cleaned according to
the manufacturer's instructions using only  recommended  cleaning
fluids every 3 months or upon erratic operation.

7.4  Sampling Train

    All remaining  sample  train  components  should  be visually
checked every 3 months and completely disassembled and cleaned or
replaced yearly.  Many items,  such as quick  disconnects,  should
be  replaced  whenever  damaged rather than checked periodically.
Normally,  the best procedure  for  maintenance in the field is to

-------
                                               Section No.  3.13.7
                                               Date July 1,  1986
                                               Page 2

use another entire  unit  such  as  a  meter  box,  sample box,  or
umbilical cord (the hose that connects  the  sample box and meter
box) rather than replacing individual components.
o
                                                                   o
                                                                   o

-------
                                                                Section No. 3.13-7
                                                                Date July 1, 1986
                                                                Page 3
            Table 7.1.  ACTIVITY MATRIX FOR EQUIPMENT MAINTENANCE CHECKS
Apparatus
  Acceptance limits
   Frequency and method
       of measurement
   Action if
 requirements
 are not met
Routine main-
tenance
No erratic behavior
Routine maintenance
performed quarterly
or after-2830 liters
(100 ft J) of opera-
tion; disassemble and
clean yearly
Replace parts
as needed
Fiber vane
pump
In-line oiler free
of leaks
Periodically check oil-
er jar; remove head
and change fiber vanes
Replace as
needed
Diaphragm
pump
Leak-free valves func-
tioning properly
Clean valves during
yearly disassembly
Replace when
leaking or mal-
functioning
Dry gas
meter
No excess oil, corro-
sion, or erratic rota-
tion of the dial
Check every 3 mo. for
excess oil or corrosion
by removing the top
plate; check valves and
diaphragm yearly and
whenever meter dial runs
erratically or whenever
meter will not calibrate
Replace parts as
as needed or re-
place meter
Rotameter
Clean and no erratic
behavior
Clean every 3 no. or
whenever ball does not
move freely
Replace
Sampling
train
No damage
Visually check every
3 mo; completely dis-
assemble and clean or
replace yearly
If failure
noted, use
another entire
meter box, sam-
ple box, or
umbilical cord

-------
o
o
o

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                                               Section No. 3.13.8
                                               Date July 1, 1986
                                               Page 1
8.0  AUDITING PROCEDURE
    An audit  is  an independent assessment of data quality.  In-
dependence is achieved if the individual(s)  performing the audit
and their standards and equipment are  different from the regular
field crew and their  standards  and  equipment.  Routine quality
assurance  checks by a field team are necessary in generation  of
good  quality data, but they are not part of the auditing  proce-
dure.  Table 8.1 at the end of this section  summarizes the qual-
ity assurance functions for auditing.
                                                         fi 7
    Based   on   the   results  of  performance  audits   '    and
collaborative tests  of Method 6, two specific performance audits
are recommended:

    1.  Audit of the analytical phase of  Method  6A, or an audit
of the sampling and analytical phase for Method 6B.

    2.  Audit of data processing for both Methods.

It is suggested that a systems audit be conducted as specified by
the quality assurance coordinator, in addition to these  perform-
ance  audits.   The two performance audits and the systems  audit
are described in detail in Subsections 8.1 and 8.2, respectively.

8.1  Performance Audits

     Performance  audits are made to evaluate quantitatively  the
quality of data produced by the total measurement system  (sample
collection, sample analysis, and data  processing).  It is recom-
mended that these audits  be performed by the responsible control
agency  once during every enforcement source test.  A source test
for  enforcement  comprises  a series of runs at one source.  The
performance audit of the analytical phase is subdivided  into two
steps:  (1)  a pretest audit which is optional, and (2) an  audit
during  the  field  sampling  and/or  analysis  phase   which  is
required.

8.1.1   Pretest  Audit of Analytical Phase Using Aqueous Ammonium
Sulfate (Optional) - The pretest  audit described in this section
can  be  used to determine the proficiency of the analyst and the
standardization of solutions in the Method 6A or 6B  analysis and
should be performed at the discretion of the agency auditor.  The
analytical phase of Method 6A or 6B can be audited  with  the use
of  aqueous  ammonium  sulfate  samples  provided  to the testing
laboratory before the enforcement  source test.  Aqueous ammonium
sulfate  samples may be prepared by the  procedure  described  in
Subsection 3.13.5 on control sample preparation.

     The  pretest  audit provides the opportunity for the testing
laboratory  to  check  the accuracy of its analytical  procedure.
This audit is especially recommended for a laboratory with little

-------
                                               Section No. 3.13.8
                                               Date July 1, 1986
                                               Page 2

or no experience with the  Method  6A  or  6B  analysis procedure
described in this Handbook.

     The  testing  laboratory should provide the agency/organiza-
tion requesting the performance test with a notification  of  the
intent to test 30 days prior to the enforcement source test.  The
testing laboratory should also request  that  the  agency/organi-
zation  provide  the  following  performance audit samples:   two
samples at a low concentration (500 to 1000 mg  SO^/dsm   of  gas
sampled  or  approximately  10  to  20 mg of ammonium sulfate per
sample)3and two samples at a high concentration (1500 to  2500 mg
S02/dsm  of gas sampled or about 30 to 50 mg of ammonium  sulfate
per sample).  This is based on an emission standard  of 1.2 Ib of
S02 per million Btu which  would  be about 1300 mg S02/dsm  at 35
percent  excess  air.   At least 10 days prior to the enforcement
source  test,  the agency/organization should  provide  the  four
audit samples.  The concentration of the two low and the two high
audit samples should not be identical.

     The testing laboratory will analyze one  sample  at  the low
concentration and one at the high concentration,  and submit their
results  to  the  agency/organization  prior  to  the enforcement
source  test.  (Note:  The analyst performing this optional audit
must be the same analyst audited during the field sample analysis
described in Subsection 8.1.2).

     The agency/organization determines the relative  error  (RE)
between  the  measured SO2 concentration and the audit  or  known
values of concentration.   The RE is a measure of the bias of the
analytical phase of Method 6A or 6B.  Calculate RE using Equation
8-1.


         RE - Cd " Ca    x 100                       Equation 8-1
                Ca
where
                                                           3
      C, = Determined audit sample concentration mg S02/dsm ,  and
                                                 3
      C  = Actual audit concentration, mg S00/dsm .
       3                                    £t

     The recommended control limit- for the  pretest  audit  is ^5
percent for both audit samples.

     If  the  results  of the pretest audit exceed 5 percent,  the
agency/organization  should have  the  tester/analyst  check  the
analytical system and repeat the audit sample  analysis  using  a
second  aliquot  of the same  audit  sample.   After  taking  any
necessary corrective action, the testing laboratory  should  then
analyze the same audit samples and report the results immediately
to  the  agency/organization  before the enforcement source  test
analysis.
                                                                   o
                                                                   o

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                                               Section No. 3.13.8
                                               Date July 1, 1986
                                               Page 3

8.1.2  Audit of Analytical  Phase  Using Aqueous Ammonium Sulfate
for  Method  6A  -   The audit described here is exactly the same
audit  promulgated  as  part of Method 6 in the Federal Register,
Vol.  49, June 27, 1984.  The agency responsible for the enforce-
ment  source test should obtain the audit samples  from  the  EPA
Quality Assurance Coordinator  in  the  respective  EPA  Regional
Office.

     The  agency should provide the tester with two audit samples
to  be analyzed at the same time as the field  samples  from  the
enforcement  source test.  The purpose of this audit is to assess
the data quality at the time of the analysis.  The relative error
(RE) for the audit samples results are determined  using Equation
8-1.  The  results of the calculated RE should be included in the
enforcement  source  test  report as an assessment of accuracy of
the analytical phase of Method 6A  during  the actual enforcement
source test.

     The two audit  samples  should be analyzed concurrently with
and  in  the  same  manner  as the set of compliance  samples  to
evaluate the technique of the analyst and the  preparation of the
standards.  The same analyst, analytical reagents, and analytical
system must be used  for  both the compliance samples and the EPA
audit samples;  if  this condition is met, auditing of subsequent
compliance analyses within  30  days  for  the  same  enforcement
agency may not be required.  An  audit sample set may not be used
to  validate different  sets  of  compliance  samples  under  the
jurisdiction  of  different  enforcement  agencies  unless  prior
arrangements are made with both enforcement agencies.
                                           3
     Calculate the concentrations in mg/dsm   using the specified
sample volume in the  audit  instructions.  (Note:  Indication of
acceptable results may be  obtained  immediately  by reporting by
telephone to the responsible enforcement agency the audit results
in  mg/dsm   and compliance  results  in  total  mg  SO2/sample.)
Include the results of both gudit samples,  their  identification
numbers,  and  the   analyst's  name  with  the  results  of  the
compliance  determination samples in appropriate reports  to  the
EPA  Regional  Office  or  the  appropriate  enforcement  agency.
Include this  information tfith subsequent compliance analyses for
the same enforcement agency during the 30-day period.

     The concentration of  the  audit  samples  obtained  by  the
analyst shall agree within 5 percent  of  the  actual  concentra-
tions.  If the 5 percent specification is not met,  reanalyze  the
compliance samples and audit  samples,   and  include  initial and
reanalysis values in tha test report.

     failure to meet tie 5 percent specification  may,  result  in
rotests until the audit  problems  are resolved.   However,  if the
audit results do not affect the  compliance or noncompiiance stat-
us of the affected  facility,  the  Administrator  may  waive the

-------
                                               Section No. 3.13.8
                                               Date July 1, 1986
                                               Page 4

reanalysis requirement, further -audits, or retests and accept the  ^J
results of the compliance test.  While steps  are  being taken to
resolve  audit  analysis  problems^  the  Administrator  may also
choose to use the data  to  determine  the  compliance or noncom-
pliance status of the affected facility.

     Note:  It is recommended that  known quality control samples
be analyzed prior to the compliance  and audit sample analysis to
optimize the system  accuracy and precision.  One source of these
samples is:

              U. S. Environmental Protection Agency
              Environmental Monitoring and Systems Laboratory
              Quality Assurance Division (MD-77A)
              Research Triangle Park, North Carolina   27711

              Attention:  Source Test Audit Coordinator

8.1.3  Audit of Sampling  and  Analytical  Phase  for Method 6B -
When Method 6B is used to  demonstrate  compliance  with a 30-day
rolling  average  standard  (e.g.,  40  CFR  60, Subpart Da), the
following audits should be conducted:

     Cylinder Gas Audit (CGA) - During  the  first 7 days of con-
tinous use of Method 6B at  the  same  source,  a  CGA  should be
conducted.  Thereafter,  a  CGA  should  be  conducted once every  X""*\
calendar quarter that Method 6B is used at the  same source.  The  (   )
purpose of the CGA is to measure the  RE  for  the  S02  and  C02   —
sampling  and analyses.  The RE should be within 15 percent.  The
testers must obtain  an  audit  gas  in an aluminum cylinder that
meets  the  requirements of EPA Protocol No. 1 (Section 3.0.4  of
this Handbook) and contains SO2 in the range of 200  to  400  ppm
and  C02 in the range of 12  percent  to  16  percent,  with  the
balance of the gas as N2.   In  addition, the tester must specify
that the gas manufacturer (1) blends moisture-free carbon dioxide
with the sulfur dioxide and  (2)  does  not  use a UV fluorescent
analyzer  to  determine the SO,, concentration  in  the  cylinder,
since a UV fluorescence SO9 signal is quenched by the presence of
co2.8
                                     g
     In  a  study  conducted  by EPA,  audit cylinders containing
sulfur dioxide  (200  to  400  ppm)  and carbon dioxide (12 to 16
percent)  were  purchased  from  nine  different  commercial  gas
manufacturers.   All  nine  cylinders ordered were to be prepared
according to EPA  Protocol  No. 1.  The purpose of this study was
to determine  whether  accurate  mixtures of S02 and C02 could be
expected from commercial gas manufacturers following EPA Protocol
No.  1  and  to  determine  if these mixtures were  stable.   The
accuracy  for  C02 was within 1.2 percent for all nine cylinders.
The  accuracy  for SO,, was within 5.2 percent for seven cylinders
and  within  9.8  percent for the remaining two  cylinders.   The
sulfur  dioxide and carbon dioxide concentrations were were found
to be stable over the entire period of the study (473 days).   In
another  study conducted by EPA,   three cylinders  containing  a
o

-------
                                               Section No. 3.13.8
                                               Date July 1, 1986
                                               Page 5

nominal  250  ppm  S02  and 10 percent COu showed the S02  to  be
stable over the entire periocLof the study (22 months).  Finally,
in a study conducted by EPA,   cylinder gases of nominal 250  ppm
S0~ and 10 percent C02 were used to audit three contractors using
Method 6B.  These audits  demonstrated that cylinder gases are an
effective means to assess the accuracy of Method 6B.

     To  conduct  the  CGA  using  the  Protocol No. 1 gases, the
following procedures should be followed:

     1.   Attach the audit gas cylinder as shown in Figure 8.1.

     2.   Open the audit cylinder until  2  times the sample flow
rate  is-^obtained on the  discharge  rotameter.   This  would  be
approximately 2.0 L/min for the intermittent  sampling train, and
approximately 60 ml/min for the continuous sampling train.  Allow
the audit  gas  to  flow  through  the  manifold for 5 minutes to
condition the manifold.

     3.    Start  the Method 6B sampling train, and adjust to de-
sired  rate.   The audit sample will be collected at a continuous
sampling rate for both the continuous  and  intermittent sampling
train.   This  is  done in an effort to minimize the use  of  the
audit gas.  The intermittent sampling  train  should  be operated
for 30 minutes.  The continuous train should  be  operated for 24
hours.

     4.   The sampling train should be set at the proper sampling
rate for the train; the audit  gas  flow  rate should then be ad-
justed  so that the discharge rotameter is reading at about equal
to the sampling rate.  This  will  ensure  that  the audit gas is
collected properly from the glass manifold.

     5.   At  the  completion  of  the run, shut off the sampling
train, then shut off the audit gas flow.

     6.    The audit sample should be recovered and  analyzed  in
the same manner as the field samples.

     7.   Calculate Ib SO2/million Btu for the Method 6B sampling
train (CMgB) using Equation 8.2.


       CM6B = 1-141 x 10    c -r-2 = Ib S00/million Btu
                                                     Equation 8-2

where

      C..-,, = Concentration measured by Method 6B, Ib SO0/
       M6B   million Btu,                              2

-------
       REGULATOR
    S02


     &


    C02


    in


    No
O
                " MALE/FEMALE GLASS JOINT
              1/8"  TEFLON
                                     GLASS MANIFOLD
                                      y
        METHOD 6B

        PROBE
           TO METHOD 6B

           SAMPLE TRAIN
                          V MALE/
                          FEMALE GLASd
                          JOINT

                            	d
                                                        V TEFLON
                                                   EXCESS TO
                                                   ATMOSPHERE
                                                                                  H202  BUBBLER
                                            ROTAMETER
Figure 8.1.  Cylinder Gas Audit  of  Method 6B.
                O
                                                                                          TJ o en
                                                                                          cu o o>
                                                                                           •

                                                                                              w
                                                                                            CD U>
O
                                                                                              oo

-------
                                               Section No. 3.13.8
                                               Date July 1, 1986
                                               Page 7

       F  = F factor (use the actual F factor or assume
            F  of 1800 for both calculations), scf of
            C02/million Btu,

     MSO  = Mass of S02 per total sample analyzed, mg of SO-, and
M
      CO  = Mass of C02 per total sample analyzed, g of C02
     8.  Calculate Ib S02/million  Btu  for  the  audit  gas (C )
using Equation 8-3.                                            a

                    7                                Equation 8-3
     Ca = 1.66 x 10" ' S02    FC   100

                         ppm'    % C02

where

        C   = Concentration in audit cylinder, Ib S00/million
         a    Btu,                                  2

     S02    = Concentration of S02 in audit cylinder, ppm,
        ppm

      % C02 = Concentration of C02 in audit cylinder, %, and

         F^ = F factor (same as above), scf of C00/million Btu.
          C                                      Z

     9.  The  auditor should then calculate the RE using Equation
8-4.

     RE = CM6B " °a   x 100                          Equation 8-4
              Ca

     10.  The RE should be within 15 percent.  The results of the
audit  should  be  included  in  the  report  as  an audit of the
accuracy of the sampling and analysis phase of Method 6B.

     S02 Analysis - During the first  7 days of continuous use of
Method  6B  at the same source, an S02 analysis audit  should  be
performed.  Thereafter, an S02 analysis audit should be conducted
once every 30 days that Methoa 6B is used  at  the  same  source.
The purpose of this audit is to measure the RE for SCw  analysis.
The RE should be within 5  percent.   The audit samples described
in Section 8.1.3 should  be  used.   The CGA and the S02 analysis
should be conducted on the same day.

8.1.4   Audit of Data Processing  - Data processing errors can be
determined by auditing the data recorded  on the field and labor-
atory forms.    The  original and audit (check) calculation should
agree within roundoff  error;  if  not, all of the remaining data
should  be  checked.    The data processing may also be audited by

-------
                                               Section No.  3.13.8
                                               Date July 1, 1986
                                               Page 8

providing the testing laboratory with specific data sets (exactly   (   }
as would appear in the field),  and  by  requesting that the data   V	/
calculation be completed and that the  results be returned to the
agency/organization.   This  audit  is  useful  in  checking both
computer programs and manual methods of data processing.

8.2  Systems Audit

     A  systems audit is an on-site  qualitative  inspection  and
review of the total measurement system (sample collection,  sample
analysis, data processing, etc.).  Initially,  a systems audit is
recommended for each  enforcement  source test, defined here as a
series  of  three  runs at one source.  After the test team gains
experience with the method, the frequency of auditing  may be re-
duced—once for every four tests.

     The auditor should have extensive  background  experience in
source sampling, specifically  with  the measurement system being
audited.  The functions of the auditor are summarized below:

     1.   Inform the  testing team of the results of pretest aud-
its,  specifying  any  area(s)  that  need special  attention  or
improvement.
     2.    Observe  procedures and techniques of the  field  team
during sample collection.

     3.    Check/verify  records  of apparatus calibration checks
and  quality control used in the laboratory analysis  of  control
samples from previous source tests, where applicable.

     4.   Record the results of the audit, and  forward them with
comments to the test team management so  that appropriate correc-
tive action may be initiated.

While on site, the auditor observes the source test team's  over-
all performance, including the following specific operations:

     1.   Setting up and leak testing the sampling train.

     2.   Preparing  and  adding the absorbing  solution  to  the
impingers.

     3.    Checking  for  constant  rate  sampling (for Method 6A
only).

     4.   Purging the sampling train (for Method 6A only).

Figure 8.2 is a suggested checklist for the auditor.
o
                                                                    o

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                                                          Section  No.  3.13.8
                                                          Date July  1,  1986
                                                          Page 9
Yes

y


/
s
/
y

if

tf
y
/
y
y
/
/
i/
\/


T /7Xd
C*c
No






















>tyst
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Comment



















#•


i\S O-r~

Presampling Preparation
1. Knowledge of process conditions
2. Calibration of pertinent equipment, in particular, the
dry gas meter, prior to each field test
On-Site Measurements
3. Leak testing of sampling train after sample run
4 . Preparation and addition of absorbing solutions to
impingers
5. Constant rate sampling (for Method 6A only)
6. Purging of the sampling train and rinsing of the
impingers and connecting tubes to recover the sample (for
Method 6A only) *>~~ •» . ..
7- Recording of pertinent process conditions during sample
collection
8. Maintaining the probe at a given temperature

Postsampling
9- Control sample analysis — accuracy and precision
10. Sample aliquoting techniques
11. Titration technique, particularly endpoint precision
12. Use of detection blanks in correcting field sample
results
13. Weighing of the CO-" absorbent
14. Calculation procedure/check
15. Calibration checks
16. Standardized barium perchlorate solution
17. Result of the audit sample

General Comments
/^/f &uc(ii- S'£*y>U£ t/J&t*e. $i*c-cc£S'ri>ti ^10*14 t*>irt
r *^Tr •
w
Figure 8.2.  Method 6A and 6B checklist to be used by auditors.

-------
                                                                Section No. 3.13-8
                                                                Date July 1, 1986
                                                                Page 10
                Table 8.1.  ACTIVITY MATRIX FOR AUDITING PROCEDURE
                                                                   O
  Audit
Analytical
 phase using
 aqueous ammon-
 ium sulfate
 (Method 6A)
  Acceptance limits
Measured RE of the
pretest audit sample
should be less than
+5% of given value
"(optional); RE for
audit during test +5
(mandatory)
  Frequency and method
      of measurement
Frequency;  Once during
every enforcement source
test

Method; Analyze audit
samples and compare
with given values
   Action if
 requirements
 are not met
Review operat-
ing technique
and repeat audit
and field sample
analysis
Analytical
 phase using
 aqueous ammon-
 ium sulfate
 (Method 6B)
Measured RE of the
pretest audit sample
should be less than
+5# of given value
"(optional)
Frequency; Once prior to
setting up a new system

Method; Measure audit
samples and compare with
given value
Review operat-
ing technique
and repeat audit
sample analysis
Sampling and
 analytical
 phase using
 cylinder gas
 audit and
 aqueous am-
 monium sul-
 fate (contin-
 uous use of
 Method 6B)
Measured RE of the
cylinder gas audit
should be less than
     (mandatory)
                 Measured RE of the
                 aqueous audit samples
                 should be less than
                 +5# (mandatory)
Frequency; Within'the
first 7 days of initial
use and every 30 days
thereafter during
continued use

Method; Perform cylinder
gas audit and compare
with given value

'Frequency; Same as above
and on the same day as
the cylinder gas audit
                                        Method; Perform audit
                                        sample analysis and
                                        compare with given value
Review operat-
ing technique
and repeat audit
O
                                                  Same as above

                                                  CQA
Data processing
 errors
The original and
check calculations
within round-off
error
Frequency; Once during
every enforcement source
test

Method; Independent
calculations, starting
with recorded data
Check and correct
all data for the
source test
(continued)
                                                                   O

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                                                                Section No. 3.13-8
                                                                Date July 1, 1986
                                                                Page 11
Table 8.1  (continued)
  Audit
 Acceptance limits
Frequency and method
    of measurement
  Action if
requirements
are not met
System audit
Operation technique
described in this
section of the Hand-
book
Frequency; Once during
every enforcement test
until experience gained,
then every fourth test

Method;  Observation of
techniques, assisted by
audit checklist,
Fig. 8.2
Explain to team
the deviations
from recommended
techniques; note
on Fig. 8.2

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o
o
o

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                                               Section No.  3.13.9
                                               Date July 1,  1986
                                               Page 1

9.0  RECOMMENDED STANDARDS FOR ESTABLISHING TRACEABILITY

    To  achieve  data of desired quality, two considerations  are
essential: the measurement process  must be in a state of statis-
tical control at the time  of the measurement, and the systematic
errors, when combined with the random variation  (errors of meas-
urement),  must  result  in an acceptable uncertainty.  To ensure
good  quality  data, it is necessary to perform  quality  control
checks  and  independent  audits  of the measurement process;  to
document these data by means of a quality control chart as appro-
priate;  and  to  use  materials,  instruments,  and  measurement
procedures  that  can  be  traced  to  an appropriate standard of
reference.

    Data must  be routinely obtained by replicate measurements of
control standard  samples  and  working  standards.   The working
calibration standards should be traceable  to  standards that are
considered primary, such as those listed below.

    1.    Dry  gas  meter  must  be calibrated against a wet test
meter  that has been verified by an independent liquid  displace-
ment method (Section 3.13.2) or by use of a spirometer.

    2.   The barium  perchlorate is standardized against sulfuric
acid.  The sulfuric acid should have been  standardized with pri-
mary  standard grade potassium acid phthalate.  The  standardized
barium  perchlorate  should  then  be  validated with an  aqueous
solution of primary  standard grade ammonium sulfate.  This makes
the  titrant  solution  traceable  to two primary standard  grade
reagents.

    3.   The audit of Method 6B is conducted with a  cylinder gas
that is traceable to  an  NBS  gas  Standard  Reference  Material
(SRM) or an NBS/EPA  approved  gas  Certified  Reference Material
(CRM) with the use of EPA Protocol No. 1.

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o
o
o

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                                                                             Section  3.13.10
                                                                             Date  July  1,  1986
                                                                             Page  1
 10.0   REFERENCE  METHODS*

 MtTHOB 6A—DrmiWIKATIOW Of SUITTJK Dl-
   oxicz.  MOISTDM. Ain>  CAMOH  DIOXISI
   EMISSIONS FROM FOSSIL Fan. COMBUSTION
   Sonnets

        1. Applicability and Principle

   1.1  Applicability. This method applies to
 the determination  of  sulfur  dioxide 
 emissions  from  fossil  fuel  combustion
 sources in terms of concentration  (mg/m')
 and in terms of emission rate (ng/J) and to
 the determination  of carbon  dioxide (CO.)
 concentration  (percent). Moisture. If  de-
 sired,  may  also  be   determined  by  this
 method.
   The minimum detectable limit, the upper
 limit, and the  Interferences of the method
 for the measurement of SOt are the same as
 for Method 6. For a  20-liter sample,  the
 method hu a  precision of 0.5 percent CO,
 for concentrations  between 2.5 and 25 per-
 cent CO,  and 1.0 percent moisture for mois-
 ture concentrations greater than 5 percent.
   1.2  Principle. The   principle of sample
 collection  is the  same  as for Method  6
 except that moisture and CO, are collected
 In addition to  SO, in the came  sampling
 train. Moisture and CO, fractions are deter-
 mined gravimetrically.

               2. Apparatus

   2.1  Sampling.  The  sampling  train  is
 shown  in Figure OA-l: the equipment re-
 quired Is the same as for Method 6. Section
 2.1. except as specified below:
   2.1.1  SO, Absorbers.  Two  30-ml midget
 impingers with a 1-mm restricted  tip and
 two 30-ml midget  bubblers with an unre-
 stricted tip. Other  types of impingers and
 bubblers,  such as Mae  West for SO, collec-
 tion and rigid cylinders  for moisture absorb-
 ers containing  Drierite. may  be used with
 proper  attention  to reagent  volumes  and
 levels, subject  to  the  Administrator's  ap-
 proval.
   2.1.3  CO. Absorber. A scalable rigid cylin-
 der or  bottle with  an  inside  diameter  be-
 tween 30 and 90 mm and a length between
 125 and 250 mm and with appropriate con-
 nections at both ends.
  NOTE For applications downstream of wet
 scrubbers,  a   heated  out-of-stacx filter
 (either boroslllcate glass wool  or glass fiber
 mat) is necessary. The filter may be a sepa-
 rate heated  unit or may be within  the
 heated portion of the probe. If the  filter is
 within the sampling probe, the filter should
 not be within IS cm of the probe inlet or
 any unheated section of the probe,  such as
 the connection  to  the  first SO, absorber.
The probe and filter should be heated to at
 least 20* C above the source  temperature.
 but not greater than ISO* C. The filter tem-
perature (i.e.. the sample gas temperature)
should be  monitored to assure the  desired
temperature is maintained. A heated Teflon
connector may be used to connect the filter
holder or probe to the first impincer.
 NOTE Mention of a brand name does not
constitute  endorsement by the  Environmen-
tal Protection Agency.
              2.2  Sample Recovery and  Analysis. The
            equipment needed for sample recovery and
            analysis is the same as required for Method
            6. In addition, a balance to measure within
            0.05 g is needed for analysis.

                          J. ReagenU

              Unless otherwise indicated, all reagents
            must  conform  to the specifications  estab-
            lished by the committee on analytical rea-
            gents  of the American  Chemical Society.
            Where such specifications are not available.
            use the best available grade.
              3.1  Sampling. The  reagents required for
            sampling are  the  same as specified  In
            Method 6. In addition, the  following ret-
            cents are required:

              3.1.1 Drtertte. Anhydrous calcium sulfate
            (CaSO.) deslccant. 8 mesh, indicating type Is
            recommended. (Do not use silica gel or simi-
            lar deslccant in the application.)
              3.1.2  CO, Absorbing Material. Accarite II.
            Sodium hydroxide  coated slllcsw 8  to  20
            mesh.
              3.2  Sample Recovery tnd  Analysis. The
            reagents needed  for  sample recovery and
            analysts are  the same as for Method 6. Sec-
            tions 3.2 and 3.3. respectively.

                        4. Procedure

            4.1  Sampling.
            4.1.1  Preparation  of Collection  Train.
          Measure 15 ml of 80  percent tsopropanol
          into the first midget bubbler and 15 ml of 3
          percent hydrocen peroxide into each of the
          first two  midget implnsers as  described in
          Method e. Insert the glacs wool into the top
          of  the  tsopropanol bubbler as shown in
          Figure 6A-1. Into  the  fourth vessel in the
          train,  the second midget bubbler,  place
          about 25 g of Drierite. Clean the outsidea of
          the bubblers and impingers. and weigh at
          room temperature (-20' C) to the nearest
          .0.1 f. Welgn the four vessels simultaneous-
          ly, and record tola I""'"1 man
            With  one end of  the CO, absorber sealed.
          place gl&ra wool in the cylinder to a depth
          of about 1 cm. Place about 150 g of CO. ab-
          sorbing material in the cylinder on top of
          the glass wool, and fill  the remaining space
          In the  cylinder with rl*"  wool. Assemble
          the cylinder as shown in Figure 6A-2. With
          the cylinder In a horizontal position, rotate
          It around the  horizontal axis. The CO, ab-
          sorelns mitrl*1 should remain in position
          durtns the rotation, and no open spaces or
                    should be  formed.  If necessary.
               more glscs wool Into  tht cylinder to
                the CO. absorbing material stable.
          Clean the outdde  of the cylinder of locee
    *  Federal  Register,  Volume  47,
       Volume  49,  No.  51,   March  14,
No.   231,  December  1,  1982  and
1984.

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                                                                              Section  3.13.10
                                                                              Date  July  1,  1986
                                                                              Page  2
dirt and moisture and weigh at room tem-
perature  to  the nearest 0.1 g.  Record this
Initial mats.
  Assemble the train as shown In Figure 6A-
1. Adjust the probe heater to a temperature
sufficient to prevent condensation isae Note
In paragraph 2.1.1). Place crushed  Ice and
water around the Lmplniers and bubblers.
Mount the COt absorber outside the crater
bath In a vertical now position with the
sample gas  Inlet  at the bottom.  Flexible
tubing, e.g..  Tygon. may be used to connect
the last SO, absorbing bubbler to the Drier-
it* absorber and to connect the Orierite ab-
corber to the CO, absorber. A second, small-
er COt absorber containing Asc&rite n may
be added In lln« downstream of the primary
COt absorber as a breakthrough Indicator.
Ascartte n  turns white  when  CO. Is ab-
sorbed.

  4.1.2  Leak-Check Procedure and Sample
Collection. The leak-check procedure and
sample collection procedure are  the tame as '
specified in  Method 0. Sections 4.1.2 and
4.1.3. respectively.
  4.2.  Sample Recovery.
  4.2.1  Moisture Measurement. Disconnect
the isopropanol  bubbler, the SCs Impinser*.
and the moisture ateorber from the cample
train. Allow  about 10 minutes for them to
reach room temperature, clean the outsidea
of loess dirt and moisture, and weigh them
simultaneously In  the came manner as In
Section 4.1.1. Record this final r«tr*-

  4.2.2  Peroxide Solution. Discard the con-
tents of the Isoproponol bubbler and pour
the contents of the mldset tmplneers Into a
leak-free  polyethylene bottle for shipping.
Hints the two midzet  tmpingers and con-
necting tubes with delonlzed distilled water.
and add the washings to the same  storage
container.
  4.2.3  CO,  Absorber. Allow the CO, ab-
sorber to warm to room temperature (about
10 minutes), clean the outside of loose dirt
and moisture, and weigh to the nearest 0.1 e
in the same manner  as in  Section  4.1.1.
Record this final macs. Discard used Ascar-
Ite II material.

  4.3  Sample Analysis. The sample analjnds
procedure for SO, U the came as specified In
Method 6. Section 4J.

             5. Calibration
  The calibrations and checks are the came
u required in Method 6. Section S.
                                     ....      o
Figure 6A-1.  Sampling train.
                                                O
                                                                      Figure 6A-2.  C02 abjorbor.
                                                                                                                      O

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                                                                                 Section  3.13.10
                                                                                 Date  July  1,   1986
                                                                                 Page  3
               6. Calculations

    Carry out calculations, retaining at least
  one extra decimal figure beyond that of the
  acquired data. Round off figures after final
  calculations.  The calculations,  nomencla-
  ture, and procedures are the same as speci-
  fied In Method 6 with the addition of the
  following:
    6.1  Nomenclature.
  C.- Concentration of moisture, percent.
  CCM« Concentration of CO,, dry basis, per-
    cent.
  M^« Initial mass  of tmplnger*.  bubblers.
    and moisture absorber, g.
  m^-Final maes of implnsen.  bubblers, and
    moisture absorber, g.
  m* - Initial mass of COi absorber, g.
  m*-Final "«»« of COi absorber, e.
  Vern^o-Equivalent volume of  CO. collected
   at standard conditions, dam'.
  VwMioEquivalent volume of  moisture col-
   lected at standard conditions. OB'.
  5.467x10-••Equivalent volume of gaseous
   CO, at standard conditions per gram. smV
   K.
  1.336xlO-*-Equlvalent volume of  water
   vapor at  standard  conditions per gram.
   sm'/g.
   6.2  COi Volume Collected.  Corrected to
 Standard Conditions.
 Vcwta»» - 5-467 x 1C"4 (m*- m*)   (Eq. 8A-1)
   6.3  Moisture Volume Collected. Correct'
 ed to Standard Conditions.
 VM^ . 1.338 x 10-' (tru- nu.)  (Eq. flA-2)
   6.4  SO, Concentration.
  7. Emission Rate Procedure.
  If the only emission meacurement desired
is in terms of emission rate of SO, (ns/J),
an abbreviated procedure may be used. The
differences between  the above  procedure
and the abbreviated procedure are described
below.
  7.1  Sample  Train. The sample train Is
the same as shown in Figure 6A-1 and as de-
scribed In Section 4. except that the dry gas
meter is not needed.
  7.2  Preparation of the Collection Train.
Follow the same procedure at in Section
4.1.1.  except do not weigh the isopropanol
bubbler, the SO, absorbing impingers or the
moisture absorber.
  7.3  Sampling. Operate the train  as de-
scribed In Section 4.1.3. except that dry gas
meter  readings, barometric pi CM lire, and
dry g&c meter temperatures need not be re-
corded.
  7.4  Sample Recovery. Fallow the proce-
dure In Section 4.2. except do not weigh the
Isopropanol bubbler,  the SO, absorbing to-
Dlngers. or the moisture absorber.
  7.5  Sample Analysis. Analysis of the per-
oxide solution is  the tame as described in
Section O.
  7.6  Calculations.
  7.6.1 SOi Maes Collected.
           (V,- V»)N
                               (Eq.aA-7)
                                (Eq.8A-
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                                                                                   Section  3.13.10
                                                                                   Date  July  1,  1986
                                                                                   Page  4
  MrmoD 6B—DrrnurDiATiott or SUITE* Di-
    oznc um CAMOW DIOXTDI DWLT AVEUCX
    EHIHIOWC PROM Fossn. FTTXL Cotavmon
    Sotntcn

         /. AfiplicatHUtv end PrineipU
    1.1  Applicability. This method applies to
  the determination of  sulfur dioxide  (8Oi)
  emissions from combustion sources in  tenni
  ol concentration (ng/m») and emission rate
  (nt/J). and (or the determination of carbon
  dioxide (CO,) concentntion (percent) on t
  dally (24 hours) bun.
    The  minim"** detectable  limits, upper
  limit,  and the Interferences for SOi meas-
  uremenu are the same as  lor  Method 8.
  EPA-tponsored  collaborative studies  were
  undertaken to determine the magnitude of
  repeatability and reproduciblllty achievable
  by qualified testers following the procedures
  in this method. The result* of the studies
  evolve from  US field  teats  including com-
  parisons with Methods 3 and  6. For meas-
  urements of emhslon  rates  from wet. flue
  gas desulfurization units in  (ng/J). the re-
  peatability (within laboratory precision) Is
  8.0 percent and the reprodueibUlty (between
  laboratory precision) Is 11.1 percent
    1.2  Principle. A gas sample is extracted
  from the sampling point In the suck  inter-
  mittently over a 24-hour or  other specified
  time period. Sampling may also be conduct-
  ed continuously If the apparatus and proce-
  dures  are appropriately modified (sea Note
  in Section 4.1.1). The SO, and CO, an sepa-
  rated  and collected In the tunpllns  train.
  The  SOi  fraction  Is  measured by the
  barlum-thonn tltratlon method, and CO, is
  determined gravtmetrically.
    2. Apparatus.
    The equipment required (or this method
  is the same as specified (or Method 6A. Sec-
  tion 2. except the tsopropanol bubbler  is not
  used. An empty bubbler for the collection of
  liquid droplets and  does  not allow direct
  contact between the collected liquid and the
  gas sample may be included In the train. For
  Intermittent operation, include an industrial
  timer-switch destined to operate in the "on"
  position at least 2 minutes continuously and
  "off" the remaining- period over a repealing
  cycle. The cycle of operation in  designated
  In the applicable regulation. At a minimum.
  the  samplinc operation should  Include at
  least 12. equal, evenly-spaced periods per 24
  hours.
   For applications downstream of tret scrub-
  bers, a heated out-of-stack filter (either tor-
  Militate class wool or (lea fiber mat) is nec-
  essary.  The  probe and (liter should  be
  heated continuously to at least 20' C above
  the sourced  temperature, but not  greater
  than 120*  C. The filter (I.e.. cample  gas)
  temperature  should be monitored to assure
  the desired temperature is maintained.

  Stainless steel sampling probes, type  316.
are not recommended for use with Method
SB because of potential corrosion and con-
tamination of  sample. Olacs probei or other
types of stainless steel, e.g.. Hasteloy or Car-
penter 20 are recommended for Ions-terra
use.
  Other samplint equipment, such as Mae
West bubblers and rigid cylinders (or mois-
ture absorption, which  requires cample or
reagent volumes other than those specified
In this procedure for full effeetiveneu may
be used, subject to the approval of the Ad-
ministrator.
                                                o
     3.
     All reagents for sampling and analysis are
   the same a* described  In Method 6A, Sec-
   tion 3. except isopropanol Is not used (or
   campunj. The hydrogen peroxide absorbing
   solution «h"n be diluted to no lea than 0
   percent by  volume. Instead of 3 percent as
   specified in Method 6. If Method BB is to be
   operated In a low  sample flow condition
   (lea than 100 ml/mln). molecular sieve ma-
   terial may be substituted (or  Asearite n as
   the CO, absorbing material. The recom-
   mended molecular sieve material is Union
   Carbide Vi« inch pellets, 5A. or equivalent.
   Molecular sieve material need not be dis-
   carded following the sampling run provided
   it Is regenerated as per the manufacturer's
   Instruction. Use of molecular sieve material
   onflow rates higher than 100 mVmln may
   cause erroneous CO, results.

                 4. Pncttiurt

     4.1  Sampling.
     4.1.1  Preparation  of Collection  Train.
   Preparation of the sample train is the same
   as described in Method flA.  Section  4.1.4.
   with the addition of the following:
     The sampling train Is assembled as shown
   In Figure oA-l, except the Isopropanol bub-
   bler is not included. The probe  must  be
   heated to a temperature sufficient to pre-
   vent water condensation and must include a
   filter (either In-sttck. out-of-stack. or  both)
   to prevent  paniculate  entrainment in the
   peroxide impingers. The electric supply for
   the probe heat should be continuous and
   separate from  the timed operation of the
   sample pump.
     Adjust the tlmer-rtrttch to operate in the
   "on" position from 2 to 4  minutes on a- 2-
   hour repeating cycle or other cycle specified
   in the applicable regulation. Other timer se-
   quences may  be  uisd with the restriction
   that the total sample volume collected is be-
   tween 25 and CO liters  for the amounts  of
   sampling  reagents   prescribed   in   this
   method.

   Add cold water to the tank until the 1m-
 plngtrs and bubblers are covered  at least
 two-thirds of their  length. TKe Impingers
 and bubbler tank must be covered and  pro-
 tected from inunu heat and  direct sue-
 light. If freeing  conditions exist,  the 1m-
 plnger solution and the water bath must be
 protected.
   NOTE Sampling may be conducted' con-
 tinuously if a low (low-rate cample pump (20
 to 40 ml/mln for the reagent  volumes de-
 scribed In this method) is usad. Then  the
 timer-twitch is not necs^iry. In addition, if
 the sample pump is designsd for  constant
 rate campling, the rate meter may be delet-
 ed. The total gas volume collected should bs
 between 23 and 80 liters for the  amounts of
•campling  reagents   prescribed  in   this
 method.
   4.1.3 Leak-Check  Procedure.  The  leak-
 check procedure is the cams as dtscrtbed in
 Method «. Section 4.1.2.
 O
o

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   4.1.3  Sample Collection. Record the Ini-
 tial dry gas meter reading. To begin sam-
 pling, position the Up of  the probe at the
 sampling  point,  connect the probe to the
 tint implnger (or filter), and ct&n the timer
 and  the sample  pump. Adjust  the maple
 flow to t constant rate of approximately 1.0
 llter/mln  as  Indicated  by the rotameter.
 Assure that the timer is operating as Intend-
 ed, i.e.,  in the "on" position for the desired
 period and the cycle repeats as required.
   Durint  the  24-hour  sampling  period.
 record the dry gas meter temperature one
 time between 8:00 *-m and 11:00 «-m-, and
 the barometric pressure.
   At the conclusion of the run. turn off the
 timer and the sample  pump, remove the
 probe from the stack, and record the final
 gas meter volume reading. Conduct a lea*.
 check as described in Section 4.1.2. If a leak
 is found, void the test run or use procedures
 acceptable to the Administrator to adjust
 the sample volume for leakage.  Repeat the
 step*  in this section  (4.1.3) for successive
 runs.
   4.2  Sample Recovery. The procedures for
 sample  recovery  (moisture measurement.
 peroxide solution, and aseartte bubbler) are
 the same as in Method 6A, Section 4.2.
   4.3  Sample Analysis. Analysis of the per-
 oxide tmpmger solutions  is the same as in
 Method 6. Section 4.3.


              5. CaJ.lbra.tion

 S.I  Metering System.
 5.1.1 Initial Calibration.  The Initial cali-
bration for the volume metennf system is
the same as for Method 6. Section 5.1.1.
 5.1.2  Periodic  Calibration  Check. After
30 days of  operation of the test  train, con-
duct a calibration check u in Section 5.1.1
above, except  for the following  variations:
(1) The leak check is not to be conducted.
(2) three or more revolutions of the dry gas
meter must be used, and (3) only two  inde-
pendent runs need be made. If the calibra-
tion factor  does not deviate by more than 5
percent  from the initial calibration factor
determined In Section  5.1.1. then  the dry
gas meter volumes obtained during the test
series are acceptable and use of the  train
can continue. If the calibration factor devi-
ates by more than 5 percent, recalibrate the
metering system as in Section 5.1.1: and for
the calculations for the preceding 30 days of
data, use the calibration factor (initial or re-
aUlbratlon) that  yields  the  lover  gas
volume for  each test run. U*e the latest cali-
bration factor for succeeding tests.
 5.2  Thermometers.    Calibrate  against
mercury-tn-glacs thermometers Initially and
at 30-day Intervals.
 5.3  Rotametar.  The  rotameter need not
be calibrated,  but should  be cleaned  and
maintained according to the manufacturer's
instruction.
  5.4  Barometer. Calibrate against a mer-
cury barometer Initially and at 30-day inter-
vals.
                                                                                      Section  3.13.10
                                                                                      Date  July  1,  1986
                                                                                      Page  5
  5.5  Barium  Perchlorate  Solution.  Stan-
d&rize  the  barium  perchlorate solution
aealnst 25 ml of standard  lulfurtc add to
which 100 nU of 100 percent icopropanol has
been added.

             S.  Calculation*

  The nomenclature and calculation proce-
dures are the t&me u In Method 8A with
the following exceptions:
P^,. initial barometric pressure for the test
    period. ""* Hg.
T.-Absolute meter  temperature  for  the
    test period. 'K.

        7. rmtwton Itatt Procedure

  The emission rate procedure 1s the same
as described In Method 6A. section 7. except
that the  timer is needed  and Is operated as
described in  this  method.

             t.  Sitlioyrcptiy
  8.1  Same as  for Method fl, citations 1
through  6. with  the addition of the follow-
ing:
  8.2  Stanley. Jon and P.R. Westlln. An Al-
ternate Method  for Stack Oas  Moisture De-
termination. Source   Evaluation  Society
Newsletter. Vol. 3. No. 4. November 1878.
  8J  Whittle. Richard N. and  PJl. Westlln.
Air Pollution Teat Report: Development and
Evaluation  of an Intermittent  Integrated
SOi/COt Emission Sampling Procedure. En-
vironmental  Protection  Agency. Emission
Standard and Engineering Division. Emis-
sion Measurement Branch. Research Trian-
gle Part. North Carolina. December 1P7B. 14
paces.
  8/t Butler.  Prank  E: J.E.  Knoll.  J.C.
Suggs. MJl. Midgett. and  W. Mason.  The
Collaborative Test of Method 6B: Twenty-
Pour-Hour  Analysis   of  SO.  and   CO
JAPCA. Vol. 33.  No. 10. October 1883.

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o
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o

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                                              Section No. 3.13.11
                                              Date July 1, 1986
                                              Page 1
11.0  REFERENCES
   1.   Butler,  Frank E.,  Joseph  E.  Knoll,   Jack  C.  Suggs,  M.
       Rodney Midgett,  and Wade Mason.  The Collaborative Test of
       Method  6B:    Twenty-Four-Hour  Analysis  of  S00 and C00.
       JAPCA, Volume 33,  No. 10, October 1983,  pp. 968-973.    ^

   2.   Federal  Register,  Volume  47,   No.   231, December 1, 1982.
       Method 6A -  Determination of Sulfur Dioxide, Moisture, and
       Carbon  Dioxide   Emissions  From  Fossil  Fuel  Combustion
       Sources   and  Method 6B - Determination of Sulfur  Dioxide
       and Carbon Dioxide Daily  Average  Emissions  From  Fossil
       Fuel Combustion  Sources.

   3.   Federal   Register,  Volume 49,  No.   51,   March  14,   1984.
       Additions and Corrections to Methods 6A and 6B.

   4.   Fuerst,   Robert   G.   Improved  Temperature  Stability  of
       Sulfur  Dioxide  Samples Collected by  the  Federal  Refer-
       ence Method.   EPA-600/4-78-018, April 1978.

   5.   Knoll, Joseph E.  and M. Rodney Midgett.   The Applica- tion
       of EPA Method 6  to  High  Sulfur Dioxide Concentra- tions.
       EPA-600/4-76-038,  July 1976.

   6.   Fuerst,  R. G.,   R. L. Denny, and M. R. Midgett.   A Summary
       of  Interlaboratory  Source Performance  Surveys  for  EPA
       Reference Methods 6 and  7  -  1977.   Available from U. S.
       Environmental Protection Agency, Environmental Monitoring
       and  Support Laboratory (MD-77), Research  Triangle  Park,
       N.C.  27711.

   7.   Fuerst,   R.   G.   and  M.  R. Midgett.  A Summary of Inter-
       laboratory Source Performance  Surveys  for  EPA Reference
       Methods   6  and   7 - 1978.  Report in preparation by U. S.
       Environmental Protection  Agency,   Environmental Monitor-
       ing  and  Support  Laboratory  (MD-77),   Research Triangle
       Park, N.C.  27711.

   8.   Zolner,   W.   J.    Quenching  in a Fluorescent  Instrument.
       Thermo Electron  Corporation,  85  First  Avenue,  Waltham,
       Mass. 17 pages.

   9.   Wright,   R.   J.  and C. E. Decker. Analysis of EPA Protocol
       No. 1 Gases  for  Use  as  EPA  Method  6B  Audit Materials.
       Project   Report   under  EPA  Contract No. 68-02-4125, June
       1986.
                                                        ,<_
                                                      V.	

-------
                                              Section No. 3.13.11
                                              Date July 1, 1986
                                              Page 2

10.  Hines, A., EPA, Environmental Monitoring Systems Laboratory,  C   J
     Research Triangle Park, NC 27711.  Unpublished research.      \~s

11.  Jayanty, R. K. M., J. A. Sokash, .R.  G. Fuerst, T. J. Logan,
     and  M.  R.  Midgett.   Validation  of an Audit Material for
     Method  6B.   Proceedings  of  APCA  International Specialty
     Conference on Continuous Emission Monitoring — Advances and
     Issues,  October 1985.
                                                                   o

-------
                                              Section No.  3.13.12
                                              Date July 1,  1986
                                              Page 1
12.0  DATA FORMS
    Blank data forms  are provided on the following pages for the
convenience  of  the Handbook user.  Each blank form has the cus-
tomary  descriptive  title centered at the top of the page.   How-
ever, the section-page documentation in the top right-hand corner
of each page of other sections has been replaced with a number in
the lower right-hand corner that will enable the user to identify
and refer  to  a  similar  filled-in form in a text section.  For
example, Form M6A&B-1.2 indicates that the form  is Figure 1.2 in
Section 3.13.1 (Methods  6A  and  B)  of  the  Handbook.   Future
revisions  of  these  forms,  if  any, can be documented as 1.2A,
1.2B, etc.  Fifteen of the  blank forms listed below are included
in this section.  Five are in the Method Highlights subsection as
shown by the MH following the form number.
    2.5 (MH)

    3.1 (MH)

    4.1


    4.2


    4.3


    4.6

    4.7 (MH)

    4.8 (MH)

    5.1 (MH)

    5.2

    5.3
Title

Procurement Log

Wet Test Meter Calibration Log

Dry Gas Meter Calibration Data Form
(English and metric units)

Pretest Sampling Checks

Pretest Preparations

Field Sampling Data Form for
Method 6A

Method 6B Sampling, Sample Recovery,
and Sample Integrity Data Form

Method   6A  Sample   Recovery   and
Integrity Data Form

Sample Label

On-Site Measurements for Method 6A

On-Site Measurements for Method 6B

Posttest Sampling Checks

Sulfur Dioxide Analytical Data Form

Control Sample Analytical Data Form

-------
                                          Section No.  3.13.12
                                          Date July 1,  1986
                                          Page 2


5.4 (MH)                 Posttest Operations                      ^^

6.1                      Method 6A and 6B Calculation  Form
                         (Conversion Factors)

6.2A & 6.2B              Method  6A  and  6B  Sulfur  Dioxide
                         Calculation Form (English and metric
                         units)

8.2                      Method 6A and 6B Checklist to Be
                         Used by Auditors
                                                                  o
                                                                  O

-------
PROCUREMENT LOG
Item description

- Qty-

Purchase
order
number

Vendor

Date
Ord.

Rec.

Cost

Disposition

Comments

              Quality Assurance Handbook M6A&B-1.2

-------
                                      WET TEST METER CALIBRATION LOG
               Wet test meter serial number
                  Date
               Range of wet test meter flow rate



               Volume of test flask V  = 	
                 Satisfactory leak check?
                 Ambient temperature of equilibrate liquid in wet test meter and reservoir
Test
number
1
2
3
Manometer
reading, a
mm hUO



Final
volume (V - ) ,
L



Initial
volume (Vj),
L



•total
volume (Vm)b,
in
L



Flask
volume (V ) ,
S
L



Percent
error,0
%



           Must be less  than 10 mm (0.4 in.)  H2O.



           Vm = V- - V, .
            ra    f    i


           % error = 100 (Vm - V0)/V0 =
                          ZQ    S   S   ^™^—i«^^^^^^"^™
  (+1%).
                                          Signature of calibration person
o
o
Quality Assurance Handbook M6A&B-2.2

                               o

-------
Date
               DRY GAS METER CALIBRATION DATA FORM (ENGLISH  UNITS)

            Calibrated by 	   Meter box number 	 Wet  test meter number
Barometer pressure, P  =
                              in. Hg   Dry gas meter temperature correction factor
Wet test
meter
pressure
drop
(Dm>'a
in. H-O



Rota-
meter
setting
(R8>,
ft3/min



Wet test
meter gas
volume
< V 'b
ft3



Dry test meter
gas volume
(vd),b ft3
Initial



Final



Wet test
meter
gas temp
,
°F



Dry test meter
Outlet
gas temp
ltd >,
o
°F



Average
gas temp
,C °F Time of run (9),d min Average ratio (Y±),e (Yr ),f 3 Dm exPressed as negative number. Volume passing through meter. Dry gas volume is minimum for at least five revolutions of the meter. c The average of t, and t, if using two thermometers; the actual reading if using one thermometer. , i o The time it takes to complete the calibration run. e With Y defined as the average ratio of volumes for the wet test and the dry test meters, Y.^ = Y +0.02 Y for calibration and Y.^ = Y +0.05 Y for the posttest checks; thus, w (td + 460°F) |Pm + (Dm/13.6)] (tw + 460°F) (Eq. 1) and Y = (Eq. 2) With Y defined as the average ratio of volumetric measurement by wet test meter to rotameter. Tolerance Yr = 1 +0.05 for calibration and Y +J3.1 for posttest checks. ri Vw (td + 4bO°F) [Pm + (Dm/13.6)] 8 (tw + 460°F) (Pm) (Rs) Y2 + Y3 (Eq. 3) and (Eq. 4) Quality Assurance Handbook M6A&B-2.4A 
-------
     Date
              DRY GAS  METER  CALIBRATION DATA  FORM  (METRIC UNITS)
           Calibrated by 	   Meter box number 	     Wet test meter  number
     Barometer pressure,  P
                         m
                             in. Hg   Dry gas meter temperature correction factor
Wet test
meter
pressure
drop
(Dm>'a
mm I^O



Rota-
meter
setting
(Rs),
cc/min



Wet test
meter gas
volume
< V 'b
L



Dry test meter
gas volume
(Vd),b L
Initial



Final



Wet test
meter
gas temp
'
°C



Dry test raeter
Outlet
gas temp
' o °c Average gas temp (td),c °C Time of run (8),d min Average ratio (Y±),e ] (tw + 273°C) (Pm) (Eq. 1) and Y = (Eq. 2) With Y defined as the average ratio of volumetric measurement by wet test meter to rotameter. Tolerance Y, 1 -H).0b for calibration and Y +0.1 for posttest checks. C' (td + 273°C) [Pm + (Dm/13.6)1000,J 8 (tw + 273°C) (Pm) (Rs) (Eq. 3) and (Eq. 4) O o Quality Assurance Handbook M6A&B-rP-s4B O' 
-------
                  FIELD SAMPLING DATA FORM  FOR METHOD 6A
Plant name
Sample location
Operator 	
Barometric pressure, mm (in.)  Hg
Probe material
Meter box number 	
Ambient temperature,  C { F)
Initial leak  check
Final leak check
      City
      Date
      Sample number
      Probe length m (ft)
      Probe heater setting 	
      Meter calibration factor (Y)
      Sampling point location 	
      Sample purge time, min 	
      Remarks
Sampling
time,
min







Total
Clock
time,
24 h








Sample
volume ,
L (ft3)







Total
Sample
flow rate
setting,
L/min
(ft3/min)








Sample
volume
metered
'
m_
L (ft5)







Vm
avg
Percent
deviation,
%







Avg
dev
Dry gas
meter
temp,
°C (6F)







Avg
Impinger
temp,
°C <°F)







Max
temp
                      V  -  V  ave
  Percent deviation =   m     m  VB
x 100 (must be within 10 percent)
                           V  avg
                            m
                                   Quality Assurance  Handbook M6A&B-4.1

-------
             METHOD 6B SAMPLING,  SAMPLE RECOVERY,  AND
                    SAMPLE INTEGRITY DATA FORM
Plant 	
Sample location
Operator 	
Run No.
Sampling period
              Initial leak check
              Final leak check 	
              Recovery date 	
              Recovered by 	
Start:
Stop:
Date
Date
Time
Time
Dry Gas Meter
Final reading 	
Initial reading 	
Volume metered 	
Dry Gas Meter Calibration Factor, Y
   L
  "L
  "L
     Rotameter
     Initial setting
     Final setting
    L or cc/min
    L or cc/min
Meter Temperature
              Barometric Pressure
                                         o
WF in. Hg
time
Probe Temperat
Initial
Final °
Moisture
1st
Final wt
Initial wt
Net wt

ure Filter
F Initial
F Final
bubbler 2nd
g
g
Total moisture
Temperature
°F
impinger
g
g
g

Ascarite
Final wt
Inital wt
Net wt
3rd impinger
g
g
g
g
time
Column
g
g
g of CO.,
4th bubbler
g
g
g
% spent
                                                                      O
     H2°2
     container no.
  RECOVERED SAMPLE (If Applicable)

                  Liquid level

                  marked
     Impinger contents

     container no.
     H20 blank

     container no.
     Samples stored and locked

     Received by 	
     Remarks
                  Liquid level

                  marked
                  Liquid level
                  marked
                       Date
                             Quality Assurance Handbook M6A&B-4.2
                                                                      O

-------
          METHOD  6A SAMPLE RECOVERY AND INTEGRITY DATA FORM
 Final wt

 Initial wt

 Net wt
 1st bubbler

	9
2nd impinger  3rd impinger

	9  	9
	g  	g
             Total moisture
 4th bubbler

	g
	_g
	g
	 % spent
     Ascarite column:
            Final wt
            Initial wt

            Net wt
                                           _g of C0
                                           % spent
                          Recovered Sample
H202 blank
container no.
Impinger contents
container no.
H2O blank
container no.
                           Liquid level
                           marked
                           Liquid level
                           marked
                           Liquid level
                           marked
Samples stored and locked

Remarks
Received by

Remarks
                                 Date
                             Quality Assurance Handbook M6A&B-4.3
                                                   (ft*

-------
SAMPLE LABEL
Plant City
Site Sample Type
Date Run Number
Front rinse LJ Front filter Q Front solution 0
Back rinse LJ Back filter O Back solution LJ
Solution Level marked 1— ) j£
Volume: Initial Final 
-------
                   SULFUR  DIOXIDE  ANALYTICAL DATA  FORM
Plant Date
Sample location Analyst
Volume and normality of barium perchlorate
Standardization blank ml (< 0.5 ml)



1
2
3



ml
ml
ml



N
N
N
N,
avg



Sample
number

1
2
3
4
5
6
Field
Blank



Sample
identification
number








Total
sample
Sample
aliquot
volume volume
' ^
ml







N/A
ml










Volume of titrant (V. ) , ml
t
1st
titration








2nd
titration









Average






V =

  Volume  for the blank must be the same as that of the sample aliquot.
b 1st titration
                                     titratlon _ 2nd titration  <0.2 ml.
  2nd titration
  Signature of analyst
  Signature of reviewer or supervisor
                                  Quality Assurance Handbook M6A&B-5.2
                                                            ,/
                                                       V

-------
               CONTROL SAMPLE ANALYTICAL DATA FORM
Plant
Analyst
                Date analyzed
                Nr
                                                                   o
                                   'Ba(Cl04)2
    Weight of ammonium sulfate is 1.3214 g?
    Dissolved in 2 L of distilled water? 	
    Titration of blank
           ml Ba(CIO.)2 (must be <0.5 ml)
Control
sample
number

Time of
analysis,
24 h

a
Titrant volume, ml
1st

2nd
• • •.
3rd

Avg

      Two titrant volumes must agree within 0.2 ml.
(ml Ba(C104)2 - ml Blank) x NBa(         25 ml x  0
                                       (control) (control
                                        sample)   sample)
        ml -
ml) x
N =
(must agree within 5%, i.e., 0.238 to 0.262)
Does value agree? 	yes  	_no
	  Signature of analyst
	  Signature of reviewer
                                                                   O
                             Quality Assurance Handbook M6A&B-5.3
                                                                    o

-------
 METHOD 6A AND 6B CALCULATION FORM (CONVERSION FACTORS)
            METER VOLUME (metric to English)
V  =	.	liter
V  = Vm (in liters) x 0.03531 ft3/liter = _ .  	 ft3

            METER TEMPERATURE (metric to English)

tffl = [tffl (°C) x 1.8] + 32 = 	 . _ °F
Tm " *n, (°F) + 46° =	' - °R

            BAROMETRIC PRESSURE (metric to English)
pbar =	• mm Hg
Pbar = Pbar ^mm HS* x °'03937 ln- Hg/mm Hg = 	 . 	 in. Hg
            METER VOLUME (English to metric)
Vm = _ .     ___ ft3
Vm = Vm (ft^> x 0.02832 m3/ft3 = . _____ m3
            METER TEMPERATURE (English to metric)
*«, -       *   °F
 m   _ _ _   _
tm = [tm (°F) - 32] x 5/9 = __ .  _ °C

T  ' *  (°C) * 273 '       •   °K
            BAROMETRIC PRESSURE (English to metric)
Pbar =__•__ in' "3
Pbar = Pbar ^in* Hg^ x 25*4 mm H9/in- Hg = ___ .  mm Hg
                         Quality Assurance Handbook M6A&B-6.1
,3
                                                      7

-------
         METHOD 6A AND 6B CALCULATION FORM  (ENGLISH UNITS)
              STANDARD METER VOLUME  (English units)
    V  -             £t-   Y =
    Vm ""_•__ — —'     _'
     111   ^^   ^^ ^^              ^^
   'bar = __•__ in. Hg, Tm =	. _°R
                                          o
  Vm(std) = 17.64 Vm Y
bar
                          Tm
dscf
            C02 VOLUME COLLECTED, STANDARD CONDITIONS

                           (English units)

           n»a£ = ___ • _ 9, mai = ___  • _ 9
V,,- (std) = 0.01930 (m _ - in  . )  =   .         dscf
 ou—                  ar    ai    —   — — — —
                                                     Equation  6-1


            C02 CONCENTRATION  (percent by volume)



Cpn  =     Vc02(std)             - 100 =__.__%
                                          O
   2       Vstd> + VC02(std)
                                                      Equation 6-4


            S02 CONCENTRATION  (English  units)


 Vt = __ . __ ml, Vtb  = _. __ ml, N = _. ____ (g-eq)/ml

Vsoln = ---  • _ ml, Va = _ _  . _ ml
     = 7.061 x 10"5  (Vt  - Vtb)N/Vsoln\_

          V fstd) +  Vnn  (std)   * Va  '
                                                      Equation 6-3
                           Quality Assurance Handbook  M6A&B-6.2A

-------
      METHOD  6A AND  6B CALCULATION FORM  (ENGLISH UNITS)


                          (continued)





              MOISTURE CONCENTRATION  (percent)



      mwf =	'  - 9'  mwi  =	' - 9


  Vw(std) = °-04707  (mwf  ~ mwi)  =  ' 	 dscf     Equation  6-2




                   VH^O(std)	 x 100  =      .     %
                     »T™         .  »»                  "™" ™~~   ""™ """"
   H2°    Vm(std) + VH20(std) + VC02(std)
              EMISSION RATE OF SO2  (English units)


                      (using meter  volumes)




             scf of C02/million Btu


                     =   -       lb S0,,/million Btu
                                                     Equation  6-5
             r. _
             C  — ,

                Cco2
                   (not using meter sample volume)
F  =         scf of C00/million Btu
 C   — — — —          £.
mcn   = 32.03 (V. - V..)N /V  , \=        .     mg of SO0 collected
 oU^            t;    "to   f soini  — — —   — —         z,

                          *  a
1V
                      Equation 6-6
        ^ (1.141 x 10"3)   m.,^  =      .       lb S00/million Btu
        C                   oUo     —   — — —      ft
                        (maf - mai)
                                                     Equation  6-7
                  SO2 CONCENTRATION (ppm)
     (ppm) =  S07           ,         .   ppm
                A       _„    ----   —

              1.663 x 10 '
                          Quality Assurance Handbook M6A&B-6.2A

-------
     METHOD 6A AND,6B CALCULATION FORM (METRIC UNITS)
            STANDARD  METER VOLUME (metric units)                   S~\
                     (using meter volumes)





                  liter x 0.001 =   .            m3
Y  =           ,  p     =        .  mm Hg, T        .   °K
     ^—   — — r —  DOJL    ""^ ^~ "^           in *~* ^~ ~"   ~~





Vm(std) = 0.,3858 VmY  Pbar = . _____ dscm



                      Tm




          C02  VOLUME  COLLECTED,  STANDARD CONDITIONS


                        (metric  units)
J"af =	• _ a/  »iai  =	•  _ g




                      -4
Vrr. (std) =  5.467  x 10   (m ,. - m . ) = .           dscm
 \**\J*y                       ClX    uJ.          "~* """* ~~

                                                    Equation  6-1






             C02 CONCENTRATION (percent by volume)






c    s       Vco2(std)         100 = __.__%


 C02 "    Vm(std)  + V   (std)


                                                    Equation  6-4





             S02 CONCENTRATION (metric units)





V. =      .     ml,  V..  =    .     ml, N =    .          (g -  eq)/ml,
  U   — —   — _~       uD    ~~   ~~ ~""         ~~~   ~~~ "~~ "~ *~~





Vsoln «	 _ ml, Va = _ _ . _ ml
          32.03  (Vt - Vtb)
                                                    mg/dscm
                                                                    o
        'm(std)     C02(std)



                                                  Equation 6-3


                       Quality Assurance Handbook M6A&6B-6.2B      ^"^

-------
        METHOD  6A AND SB CALCULATION FORM (METRIC UNITS)


                           (continued)





                MOISTURE CONCENTRATION (percent) ,
   m
    wf
                • _ 9' m
                       wi   --- • _
Vm(std) " 1'336 x
                          (mwf - mwi> '
                                                    dscm

                                                    Equation 6-2
     . _

     2
     z
                                           x 100 =
             V       + V         + V
             vm(std)   vH20(std)   vC02(std)
               EMISSION RATE OF S02 (metric units)


                      (using meter volumes)
                                                             %
                                                    Equation 6-5
   F  =
    c
    SO
                      -7
        _ .	x 10   dscm of C02/J
                        (not using meter volumes)
F  =   .
 c   —
mso2 - 32-03
                   _

               x 10   dscm of CO0/J
             (Vt - V,b) N/Vsoln\= 	 .  	 mg of S02 collected
ESO  = Fc t1'
                         
                                                     Equation 6-6
                                                     Equation 6-7
                           Quality Assurance Handbook M6A&B-6.2B


-------
METHOD 6A  AND  6B CHECKLIST  TO BE  USED BY AUDITORS
                                                                    o
Yes
No
Comment
                Presampling Preparation
       1. Knowledge of process conditions
       2. Calibration of pertinent equipment, in particular, the
          dry gas meter, prior to each field  test
                  On-Site Measurements

       3. Leak testing of sampling train  after sample run
       4. Preparation and addition of absorbing solutions to
          impingers
       5- Constant rate sampling (for Method 6A only)
       6. Purging of the sampling train and rinsing of the
          impingers and connecting tubes  to recover the sample (for
          Method 6A only)

       7- Recording of pertinent process  conditions during sample
          collection
       8. Maintaining the probe at a given temperature
                                                                               O
                       Postsampling

       9. Control sample analysis--accuracy and precision
      10. Sample aliquoting techniques
      11. Titration technique,  particularly endpoint precision
      12. Use of detection blanks in correcting field sample
          results
      13. Weighing of the C0_ absorbant
         . Calculation procedure/check
      15. Calibration checks
      16. Standardized barium perchlorate  solution
      17. Result of the audit sample
                   General Comments
                                                              -8-2O
                                   Quality Assurance  Handbook M6A&B

-------
                                                  Section No. 3.14
                                                  Date July 1, 1986
                                                  Page 1
                         Section 3.14
         METHOD 7A - DETERMINATION OF NITROGEN OXIDE
              EMISSIONS FROM STATIONARY SOURCES
         (Grab Sampling - Ion Chromatographic Method)
                           OUTLINE
  Section
SUMMARY
METHOD HIGHLIGHTS
METHOD DESCRIPTION
   1.  PROCUREMENT OF APPARATUS
       AND SUPPLIES
   2.  CALIBRATION OF APPARATUS
   3.  PRESAMPUNG OPERATIONS
   4.  ON-SITE MEASUREMENTS
   5.  POSTSAMPLING OPERATIONS
   6.  CALCULATIONS
   7.  MAINTENANCE
   8.  AUDITING PROCEDURES
   9.  RECOMMENDED STANDARDS FOR
       ESTABLISHING TRACEABILITY
  10.  REFERENCE METHOD
  11.  REFERENCES
  12.  DATA FORMS
Documentation
     3.14
     3.14
Number of
  pages
     2
     8
3.14.1
3.14.2
3.14.3
3.14.4
3.14.5
3.14.6
3.14.7
3.14.8
3.14.9
3.14.10
3.14.11
3.14.12
10
14
6
7
11
6
2
6
1
3
2
12

-------
                                                    Section No.  3.14
                                                    Date July 1,  1986
                                                    Page 2
                               SUMMARY
                                                                      o
    A gas sample is extracted from the  sampling  point in the stack.
The  sample  is collected in an evacuated 2-liter round bottom  boro-
silicate  flask containing 25 ml  of  dilute  sulfuric  acid-hydrogen
peroxide  absorbing  reagent.  The nitrogen oxides, NO and NC>2, react
with  the absorbing reagent to form nitrate ion which is analyzed  by
ion chromatography (1C).  The  method  does  not  respond  to nitrous
oxide, N20.

    The reactions  that  describe  absorption of the NO  are distinct
    NO and N0«.  The common featu
of nitrate, N03~, as nitric acid,

    The  absorption  of  NO involves an oxidation-reduction  reaction
where the  oxidizing  agent is the acidic hydrogen peroxide solution.
The two half reactions are:
for NO and N0«.  The common feature of the reactions is the formation
               ~
and
              3H2°2 + 6H+ + 6e~ = 6H2°
        2ND + 4H0 = 2N0~ + 9H+ + 6e
                                                                     O
and the overall reaction is:

        2NO + 3H2°2 = 2NCi3~ + 2H+ + 2H2°-

    The absorption of N02 presumably involves the reaction with water
to  form  nitric  acid and NO.  N0« reacts with water to form  nitric
acid and nitrous acid, HN02:

              2N02 + H20 = HN03 + HN02.

    The nitrous acid is unstable and decomposes:

              3HN02 = 2NO + HN03 + H20.

    The observed reaction is the sum of the two reactions above:

              3N02 + H20 = 2HN03 + NO.

    Absorption of N02 proceeds  faster  than absorption of NO because
N02  is  more  soluble in solution, where reaction occurs.   In  this
respect, it should be noted  that  absorption of NO is quickened as a
consequence of reaction with oxygen also present within the flask:

              2NO + 02 = 2N02.

   If the gas being sampled  contains  insufficient  oxygen  for  the
conversion of NO to N02, then  oxygen  should  be introduced into the —^
flask by  one  of  three  methods: (1) before evacuating the sampling(   )

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                                                    Section No. 3.14
                                                    Date July 1, 1986
                                                    Page 3

flask,  flush it with pure cylinder oxygen,  and  then  evacuate  the
flask to 75 mm (3.0  in.) Hg absolute pressure or less; or (2) inject
oxygen into the flask after sampling; or (3) terminate  sampling with
a minimum of 50 mm (2.0 in.) Hg vacuum remaining in the flask, record
this final pressure, and then open  the flask to the atmosphere until
the flask pressure is almost equal to atmospheric pressure.

    Method 7A is applicable to  the  measurement  of  nitrogen oxides
emitted from stationary sources.  It may be used as an alternative to
Method 7 (as defined in 40 CFR Part 60.8(b)) to determine  compliance
if  the  stack  concentration  is within the analytical  range.   The
analytical range of the method is from 125 to 1250  mg NO , expressed
as  NO,,,  per  dry  standard  cubic meter (65 to  655  ppm").   Higher
concentrations  may  be  analyzed by diluting the sample.  The  lower
detection limit is approximately  19  mg/m   (10  ppm),  but may vary
among instruments.

    The method description  which follows is based on the method that
was promulgated on' December 8, 1983.

    Section  3.14.10  contains  a  copy of Method 7A,  and blank data
forms are provided in Section  3.14.12  for  the  convenience  of the
Handbook user.

    Note;    Because  of  similarities  between Method 7A and Method 7
sampling equipment and procedures, in most cases only the differences
in Method 7A are presented in  detail  in  this section (3.14).  How-
ever,  all tasks are shown in the activity  matrices  and  data sheets
needed to perform  Method 7A are included,  whether or not differences
occur in the written descriptions.   Other  Method  7A procedures are
referenced  to  the  corresponding description in Section 3.6, Method
7.  This is done for both time savings to the reader and cost savings
to the Government.

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                                                    Section No. 3.14
                                                    Date July 1, 1986
                                                    Page 4
                          METHOD HIGHLIGHTS
o
    Section  3.14  (Method  7A)  describes the required procedure for
sampling and analyzing of nitrogen oxides emissions  from  stationary
sources.   For the method, a grab sample is extracted from a point in
the stack, and collected in a previously evacuated flask containing a
sulfuric   acid-hydrogen   peroxide  absorbing  solution.   With  the
exception  of  nitrous  oxide, the nitrogen oxides  are  oxidized  to
nitrate which is analyzed by ion chromatography  (1C).   Results  are
expressed   as   concentrations   of  nitrogen  dioxide  (N02).   The
applicable  regulation  should  be  consulted  to  determine  whether
additional  measurements, such as velocity or 02 determinations,  are
required.

    The  absorbing reagent for EPA Method 7A has a sulfuric acid con-
centration  one-tenth  that  of EPA Method 7.  In all other respects,
the sampling train and sampling procedures of EPA Method 7A are iden-
tical to those of  EPA  Method  7.   Sample preparation involves only
dilution  to  reach  a  measurable concentration range  for  the  ion
chromatograph.

    Ion chromatography  is  a  relatively  recent analytical develop-
ment.   The  reader  is  referred,2to  the  literature  for  detailed
descriptions  of  the  subject. ~    Small, et  al.,   developed  th
technique  using the principles of ion  exchange  chromatography
conductimetric  detection.   Previous  attempts  to  use this type
detection were unsuccessful because of the presence of the backgroun
electrolyte used for  elution  of  the ionic species.  Small, et al.,
used a novel combination of resins  to  separate the ions of interest
and neutralize the eluent from the background.

    The  aqueous sample is introduced into a fixed-volume sample loop
by using a plastic  syringe.   Once  injected,  the sample is carried
through  a  separation  column  at different rates according to their
relative affinities for the resin and the  eluent  and  are therefore
separated into discrete bands.   The  separated  ions are then passed
through a post-separation suppressor device, a source of hydrogen ion
(H ), which converts the eluent ions into a less conducting weak acid
while converting the analyte  ions  into  a  highly  conducting form.
This permits  the  use  of  a  conductivity  cell as a very sensitive
detector of all ionic species.

    Gjerde, et al.,   described a modified ion chromatographic method
that eliminatesthe  need  for  a  suppressor  device.   Anions  are
separated  on  a column containing an anion-exchange resin with a low
exchange capacity.   Because  of  the  low  capacity,  a  very dilute
solution of an aromatic organic acid salt may be used as  the eluent.
The conductance of the eluent is sufficiently low that no suppression
is needed.

    For Method  7A,  either  suppressed  or  non-suppressed 1C mayf~\
used.    The   basic  ion  chromatograph  will  have  the   follow\,	J
components:

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                                                    Section No. 3.14
                                                    Date July 1, 1986
                                                    Page 5

     (a)  sample injection device,

     (b)  anion separation column,

     (c)  anion suppressor column, either packed bed or fiber
         type (not required for non-suppressed 1C),

     (d)  conductivity detector, and

     (e)  recorder.

     Two  critical aspects of Method 7A are (a) the measurement of the
gaseous  sample volume, and (b) the preparation  of  the  calibration
standards for the ion chromatograph.  Analysts are advised to observe
specified  procedures  carefully  at  these  points  of  the  method.
Analysts performing the  method  should be well trained in the use of
the  ion chromatograph.

     Collaborative testing of EPA Method  7A  has  not been performed.
However, from a technical standpoint, it can  be  expected  that  EPA
Method 7A will  exhibit  accuracy  and  precision  as good as, if not
better than, EPA Method 7.

     The four  blank  data  forms  at  the  end of this section may be
removed from the Handbook and used in the pretest, test, and posttest
operations.  Each form has a subtitle (e.g.,  Method  7A, Figure 3.1)
to assist the  user in finding a similar completed form in the method
description (Section 3.14.3).   On the blank and filled-in forms, the
items/parameters that can  cause  the  most  significant  errors  are
designated with an asterisk.

1.   Procurement of Apparatus and Supplies
     Section  3.14.1  (Procurement  of  Apparatus and Supplies)  gives
specifications,  criteria,  and  design  features  for  the  required
equipment and materials.  The sampling apparatus  for  Method  7A has
the  same design features as that of Method 7.  Section 3.14.1 can  be
used as a guide for procurement  and  initial checks of equipment and
supplies.  The activity matrix (Table 1.1) at the  end of the section
is a summary of the details given  in  the  text and can be used as a
quick reference.

2.   Pretest Preparations
     Section 3.14.2  (Calibration of Apparatus) addresses the required
calibration  procedures and considerations for the Method 7A sampling
equipment (same as Method 7) and analytical equipment (the ion chrom-
atograph).   Required accuracies for each component are also included.
A pretest  sampling  checklist  (Figure  3.1  in Section 3.14.3) or a
similar form should be used  to  summarize  the calibration and other
pertinent pretest data.  The volume of each collection  flask must be
determined with  stopcock  in  place.   This  volume  measurement  is
required only on the initial calibration,   provided  the  stopcock is
not changed.   The  calibration section may be removed along with the

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                                                    Section No.  3.14
                                                    Date July 1,  1986
                                                    Page 6

corresponding sections  from  the  other  methods  and  made  into  a/"""\
separate quality assurance  reference  manual  for  use  by personnel \)
involved in calibration activities.

    Section 3.14.3 (Presampling Operations) provides  the tester with
a guide  for  equipment  and supplies preparation for the field test.
With the  exception of the preparation of certain reagents, these are
the same as for Method  7.   A  pretest preparation form (Figure 3.2,
Section  3.14.3)  can  be used as an equipment checkout  and  packing
list.  The flasks may be charged with the absorbing  reagent  in  the
base laboratory.   The method of packing and the use of the described
packing containers should  help protect the equipment, but neither is
required by Method 7A.

    Activity matrices for the calibration  of  equipment and the pre-
sampling operations (Tables 2.2 and 3.1) summarize the activities.

3.  On-Site Measurements
    Section  3.14.4   Ton-Site  Measurements)  contains  step-by-step
procedures  for  sample  collection  and for sample recovery.  Sample
collections  are the same as for Method  7;  sample  recovery  proce-
dures differ slightly  from  Method  7 in that the sample pH does not
have  to be checked and adjusted.  The on-site checklist (Figure 4.3,
Section 3.14.4) provides the tester  with  a quick method of checking
the  on-site  requirements.   When high negative stack pressures  are
present, extra  care  should be taken to purge the leak-tested sample ^^^
system and to be sure  the  flask  is  £  75  mm  (3 in. ) Hg absolute^   N
pressure  prior to testing.  Also, the 16-hour sample residence  timeV __ J
in  the flask must be observed.   Table  4.1   provides  an  activity
matrix for all on-site activities.

4.  Posttest Operations
    Section  3.14.5  TPostsampling  Operations)  gives  the  posttest
equipment  procedures  and a step-by-step  analytical  procedure  for
determination of NO , expressed  as NO^-  Posttest calibration is not
required  on any of the sampling equipment.  The posttest  operations
form (Figure 5.1, Section 3.14.5) provides  some key parameters to be
checked by the tester  and  laboratory  personnel.   The step-by-step
analytical procedure description  can  be  removed  and  made  into a
separate  quality  assurance  analytical  reference  manual  for  the
laboratory personnel.  Analysis of calibration standards is conducted
in conjunction  with  the  analysis  of  the  field  samples.  Strict
adherence to Method 7A analytical procedures must be observed.

    Section  3.14.6  (Calculations)  provides  the  tester  with  the
required equations, nomenclature,  and  significant  digits.   It  is
suggested  that  a  calculator be used, if available, to  reduce  the
chances of calculation error.                                        '.:;
    Section 3.14.7 (Maintenance) provides the tester with a guide for
a maintenance program.  This program  is  not  required,  but  should
reduce equipment malfunctions.   Activity  matrices (Tables 5.1,  6.
                                                                   ly*->.

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and  7.1)  summarize all postsampling,  calculation,
activities.
5.
                                                    Section No. 3.14
                                                    Date July 1, 1986
                                                    Page 7

                                                     and  maintenance
    Auditing Procedure
    Section 3.14.8 (Auditing Procedure)  provides  a  description  of
necessary activities for conducting performance  and  system  audits.
When Method 7A is used  to  demonstrate  compliance with an EPA poll-
utant  emission  standard,  a  performance  audit is required  to  be
conducted of the analytical phase of the method.  The data processing
procedures  and  a checklist for a systems audit are also included in
this section.  Table 8.1 is an activity  matrix  for  conducting  the
performance and system audits.

    Section   3.14.9   (Recommended   Standards    for   Establishing
Traceability) provides the primary standard  to  which  the  analysis
data should be traceable.

6.  References
    Section  3~.14.10  contains  the promulgated  Method  7A;  Section
3.14.11  contains  the references  cited  throughout  the  text;  and
Section 3.14.12 contains copies of data forms recommended  for Method
7A.
                                                  !<*
                                                    -il

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                                                Section No. 3.14
                                                Date July 1, 1986
                                                Page 8
                     PRETEST SAMPLING CHECKS
                     (Method 7A, Figure 3.1)

Date	  Calibrated by 	

Flask Volume
Flask volumes measured with valves?  	 yes  	 no
Volume measured within 10 ml of actual volume?* 	 yes 	 no

Temperature Gauge
Was a pretest temperature correction used? 	 yes 	 no
If yes, temperature correction 	 (within 1°C (2°F)
   of reference values for calibration and within HH 2°C
   (4°F) of reference values for calibration check).

Vacuum Gauge
Was gauge calibrated against a U-tube mercury manometer (if it
   was a mechanical gauge)?* 	 yes 	 no 	 not applicable

Barometer

Was the pretest field barometer reading within 2.5 mm (0.1 in.) Hg
   of the mercury-in-glass barometer? 	 yes  	 no
 o
o
*Most significant items/parameters to be checked.
o

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                                               Section No.  3.14
                                               Date July 1,  1986
                                               Page 9
                      PRETEST PREPARATIONS

                    (Method 7A, Figure 3.2)
Apparatus check
Probe
Glass liner
clean
Heated properly*
Leak checked
Collection Flask
Clean
Leak checked
Temperature
gauge
Evacuation System
Leak-free pumps
Manifold and
tubing
U-tube manometer
Barometer
Reagents
Water
Absorbing solu-
tion*
Sample Recovery
Dropper or burette
Sample bottles
Pipette, 25-ml
Acceptable
Yes





NO





Quantity
required





Ready
Yes





No





Loaded
and packed
Yes





No





*Most significant items/parameters to be checked.

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                                                Section No.  3.14
                                                Date July 1,  1986
                                                Page 10
                       ON-SITE MEASUREMENTS
                     (Method 7A, Figure 4.3)
Sampling
Volume of 25 ml of absorbing solution** placed in flask?
Flask valve stopper in purge position?
Sampling train properly assembled?
  Leak free?* 	  Stopcock grease used?
  Type? 	
Flask evacuated to £75 mm (3 in.) Hg pressure?
  Leakage from manometer observation?*	
  (e.g., maximum change in manometer of £10 mm (0.4 in.)
  Hg/min)     ,	
Initial pressure of flask recorded?* 	
Initial temperature of flask recorded? 	
Probe purged before sampling? 	
Sample collected properly?* 	
Flask shaken for 5 min after collection and disassembly from
  train?* 	
Samples properly labeled and sealed and stored for shipment?
Sample Recovery
Samples allowed to remain in flasks for minimum of 16 h?*
Final flask temperature and pressure recorded?* 	
o
Sample transferred to leak-free polyethylene bottle? 	
Flask rinsed twice with 5-ml portions of water and rinse
  added to bottle containing sample? 	
*  Most significant items/parameters to be checked.
** Note that absorbing solution for Method 7A is different from
   that of Method 7.
                                                                  O
                                                 f.lt'l

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                                                Section No. 3.14
                                                Date July 1, 1986
                                                Page 11
                       POSTTEST OPERATIONS
                     (Method 7A, Figure 5.1)

Reagents
Sodium nitrate dried at 105° to 110°C for a minimum of 2 hours
  before use? 	
Stock standard solution (sodium nitrate) less than 1 month old?
Sample Preparation
Has liquid level noticeably changed?*
  Original volume 	  Corrected volume 	

Analysis
Standard calibration curve prepared?* 	
All calibration points within 7 percent of linear calibration
  curve?* 	
Reagent blanks made from absorbing solution or eluent solution?

Same injection volume for both standards and samples? 	
Duplicate sample values agree within 5 percent of their mean?

All analytical data recorded on checklist and laboratory form?
* Most significant items/parameters to be checked.

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o
o
o

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                                                   Section No. 3.14.1
                                                   Date July 1, 1986
                                                   Page 1
 1.0   PROCUREMENT OF APPARATUS AND SUPPLIES
     A  schematic of  the  sampling train used for  Method 7A is shown in
 Figure 1.1.   The  train  and  sampling procedures are identical to those
 for  Method  7.  The sample  recovery procedures and equipment are also
 identical, with the exception that there is  no  need  to  check  and
 adjust the   pH   of the  samples.   The  analytical  procedures  and
 equipment involved  are  different.

     Specifications,  criteria, and/or  design  features  are  given in
 this section to aid in  the  selection  of  equipment or any components
 that are different   from  those  in  Section  3.6.1.   Procedures and
 limits (where  applicable)  for  acceptance  checks  are also given.
 Alternative   grab  sampling systems or equipment capable of measuring
 sample volume to within 2% and collecting a sufficient sample volume
 to allow analytical repeatability  to  within  5%  may be acceptable,
 subject to approval.

     During the procurement  of equipment and supplies, it is suggested
 that a procurement  log  be used to record the descriptive title of the
 equipment, identification number  (if applicable), and the results of
 acceptance   checks.  An example of a procurement log is shown in Fig-
 ure  1.2.    A blank copy of this form is provided in Section 3.14.12
 for  the convenience of  the  Handbook user.  Calibration data generated
 in the acceptance check are to  be  recorded  in the calibration log
 book.

     The following equipment is that which  is  specified in Method 7A
 and  has not  already been   described  in  Section 3.6.1 for Method 7.
 Table   1.1   at the  end  of this section summarizes  quality  assurance
 activities for the   procurement  and  acceptance of all apparatus and
 supplies for Method 7A  including the equipment described  in  Section
 3.6.1.

 1.1  Analysis

     For the  analysis, the following equipment is needed.  Alternative
 instrumentation   (and   corresponding  procedures)  will  be  allowed,
 provided the  calibration precision  discussed  in  Section 3.14.2 and
 acceptable accuracy can be  met.

 1.1.1   Volumetric   Pipets  - Class-A volumetric pipets are  required.
 For making up the calibration  standards,  pipets  of  the  following
 sizes  are needed:  one 1-ml,  one 2-ml, one  4-ml,  one  6-ml,  and one
 10-ml.    Enough 5-ml pipets  are  needed  for  preparing  calibration
 standards,  blanks,  and  samples.

 1.1.2  Volumetric Flasks -  Two  Class-A  50-ml volumetric flasks are
needed  for  each   sample,   and one Class-A 50-ml volume'tric flask is
needed  for each standard  and  each blank.  Also required are Class-A
200-ml  and  Class-A 1000-ml  sizes.   Additional  volumetric  flasks
 (50-ml) may be required for audit samples and for dilution of samples
having concentrations in excess of the 'highest standard.

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   PROBE
   A
   T
 FILTER
FLASK VALVE
                                                                               SQUEEZE CULQ

                                                                             :?.'.? VALVE

                                                                                   PUMP
/
                                   FLASK
                              FLASK SHIELOJ \
                                                THEf&CMETEfl
              Figure  1.1.    Method 7A  evacuated flask sampling  train
                                                                        TJ O OT
                                                                        O O CD
                                                                       IQ rt- O
                                                                        0) (D rt
                                                                            H-
                                                                        tOCj O
                                                                          C 3
o
                 O
                                                                                                            (-• •
                                                                                                            x
                                                                                                              CO
                                                                                                            I-1 •
                                                                                                            VO H1
                                                                                                            03 ifk
                      o

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Item description
J~\C~\)c, fatfrry*3l4
-------
                                                   Section No.  3.14.1
                                                   Date July 1, 1986
                                                   Page 4
1.1.3  Analytical Balance - One analytical balance that weighs to 0
mg and a set of Class-S calibration weights  to check the accuracy of
the balance (+_ 0.3 mg) upon receipt are needed.  The  balance  should
be serviced or returned to the manufacturer  if  agreement  cannot be
met.
                                                                   •iO
1.1.4  Ion Chromatograph - The ion  chromatograph  should, at a mini-
mum, have the components described below.

    Sample Injection Device - This device must be capable of deliver-
ing a reproducible volume of sample to the ion chromatograph.

    Columns - The ion  chromatograph  should  have an anion separator
column capable of giving duplicate results within 5 percent  of  mean
value and of resolving the  nitrate  ion  from  sulfate  ion and from
other  species  present.   Both  the  Dionex  HPIC-ASC fast run anion
column  for suppressed 1C and the Wescan 269-029 Anion/R  Column  for
non-suppressed  1C  have been demonstrated to give acceptable  separ-
ation.  If suppressed 1C is to be used, an anion suppressor column is
required.  The  Dionex  AFS  anion  fiber suppressor (recommended) or
ASC-1 general purpose suppressor may be used.  Suppressor columns are
generally produced as proprietary items; however,  one can be made in
the  laboratory using the resin available from BioRad  Company,  32nd
and Griffin Streets, Richmond, California.

    Pump  -  The pump must be capable of maintaining a steady  eluent
flow as required by the system.

    Flow Gauges - These must  be  capable  of measuring the specified
eluent flow rate.  It is recommended  that  the  gauge  be calibrated
upon receipt.

    Conductivity Detector with Temperature  Compensation  - It should
be capable of giving responses that can be integrated  with a precis-
ion of  +_  5  percent.   It is recommended that the detector be cali-
brated according to manufacturer's procedures prior to initial use.

    Recorder - It should be compatible with the output voltage of the
detector.

1.2  Reagents

    Unless otherwise indicated,  it  is  intended  that  all reagents
conform  to  the  specifications  established  by  the  Committee  on
Analytical Reagents of the  American  Chemical  Society  (ACS), where
such  specifications  are  available;  otherwise,  use the best grade
available.

1.2.1  Sampling - To  prepare  the absorbing solution, cautiously add
2.8  ml  concentrated  HoS04  to a 100~ml flask containing water (see
specifications in Subsection 1.2.3 below), and dilute  to volume with
mixing.   Add  10  ml  of this  solution,  along  with  6  ml  of  3%
                                                                      o

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                                                   Section No. 3.14.1
                                                   Date July 1, 1986
                                                   Page 5

hydrogen peroxide  that  has  been freshly prepared from 30% hydrogen
peroxide,  to  a  1-liter  flask.   Dilute  to volume with water (see
Subsection 1.2.3), and mix well.  The absorbing solution must be used
within  1  week of its preparation and, if possible, within 24 hours.
Store in a dark-colored bottle.  Do not  expose  to  extreme  heat or
direct  sunlight.   Refrigerate  the 30% hydrogen peroxide  solution.
Note; The H2S04 content of this absorbing solution  is  10 times less
than that used for Method 7.  The solution is prepared in this manner
to  avoid interference from sulfate ions during the analysis by 1C.

1.2.2   Sample  Recovery  -  Use  ASTM  D1193-82, Type III water (see
Subsection   1.2.3)  for  sample  recovery  and   in   making  various
solutions.   At the  option  of  the  analyst,  the  KMnO.  test  for
oxidizable organic matter may be omitted whenever high concentrations
of  organic matter are not expected to be present.

1.2.3  Analysis  -  For  the  analysis,  the  following  reagents are
required.

    Water  - Water should be used which conforms with  ASTM   specifi-
cation D1193-82> Type III.  Type III water is prepared  by  distilla-
tion,  ion   exchange,  reverse  osmosis,  or  a combination   thereof,
followed by  polishing with a 0.45 vm membrane filter.  The specifica-
tions for Type III water are shown below.

           Specifications for ASTM D1193-82, Type III Water

          Total matter, max., (mg/L)           1.0

                                               1.0
Electrical conductivity, max.,
  (vmho/cm) at 25 C

Electrical resistivity, min.,
  (ymho/cm) at 25

pH at 25°C

Minimum color retention time
  of KMn04, (min)

Maximum soluble silica, (vig/L)
                                               1.0
                                         6.2 to 7.5
                                               10
                                               10
Note;  Mention of "water"  anywhere  in this Section (3.14) refers to
ASTM  D1193-82,  Type  III water as described above.  By using  water
from the same source for making reagents, calibration standards,  and
eluents for the ion chromatograph, the effects of trace quantities of
nitrate  in the water will be negated with regard to sample analysis.
Therefore, a water blank correction is  not necessary in the develop-
ment of the calibration curve.
                                                ;/
                                                r

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                                                   Section No.  3.14.1
                                                   Date July 1,  1986
                                                   Page 6

    Sodium Nitrate - Dry an adequate amount of sodium nitrate (NaN03)(  j
at 105  to 110 C for a minimum of 2 hours just prior to preparing tttev—/
standard solution.  (The  analyst should note that potassium nitrate,
KNO,j, is used in EPA Method 7; KNCU is an acceptable alternative  for
Method 7A. )                       J                                   ..

    Stock  Standard  Solution, 1 mg NO^/ml  -  To  prepare,  dissolve
exactly 1.847 g of dried NaNO3 (or  2.198  g of dried KN03) in water,
and dilute to 1 liter in a volumetric flask; mix well.  Tnis solution
is stable for 1 month and should not be used beyond this time.

    The  use  of  old  solution  may cause results to be biased high.
Solutions are readily  contaminated  by  microorganisms  that feed on
nitrate ion.  Unquantified  loss  of  nitrate  ion  from the standard
solution causes the high bias.

    Working  Standard Solution, 25 yg NO^/ml - Dilute  5  ml .of  the
standard solution to 200 ml with water in a volumetric flask, and mix
well.

    Eluent  Solution  -  Use an eluent appropriate to the column type
and capable of resolving nitrate ion from  sulfate  and other species
present.   The  following  eluents  have been  demonstrated  to  give
acceptable separation:

Suppressed  1C — 0.0024M Na2C03/0.003M NaHC03.   To  prepare,  weigh/^N
1.018  g  of  sodium  carbonate  (Na2C03)   and  1.008  g  of  sodiuif  )
bicarbonate (NaHC03), and dissolve in 4 liters of water.             ^~^

Non-Suppressed  1C  —  0.007M  p-hydroxybenzoic acid,  pH  8.4.   To
prepare, weigh 3.867 g  p-hydroxybenzoic  acid,  and  dissolve  in  4
liters of water.  Adjust to pH 8.4 with lithium hydroxide.

    Quality Assurance Audit Samples - Same as required  by  Method  7
(Section 3.6.8).
                                                                    o

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                                                              Section No. 3.14.1
                                                              Date July 1, 1986
                                                              Page 7
                  TABLE 1.1.   ACTIVITY MATRIX FOR  PROCUREMENT OF APPARATUS
                              AND SUPPLIES

Apparatus/
supplies
Probe
Collection
flask
Flask valve
Temperature
gauge
Vacuum line
tubing
Vacuum gauge
Vacuum pump
Squeeze bulb
Volumetric
pipettes
Acceptance criteria
Borosilicate glass
stainless steel, or Tef-
lon tubing capable of
removing moisture
condensation
Two-liter borosilicate
glass round bottom, short
neck w/24/^0 standard
taper opening
Borosilicate glass T-bore
stopcock w/24/40 standard
taper male joint (joint
connection to be made by
glassblower)
Dial- type, capable of
measuring from -5 to
•f50°C within 1°C
Capable of withstanding
75 mm absolute pressure
U-tube manometer, open
end,-l m with 1-mm divi-
sions
Pump capable of pulling
vacuum of 75 nun Hg or
less
Rubber, one way
1-, 2-, H-, 5-, 6-, 10-,
25-ml Class-A glass and
graduated 5 -ml
Frequency and method
of measurement
Upon receipt, visually
check for cracks or
flaws and heating capa-
bility
Upon receipt, visually
check, and leak check
Visually check upon
receipt
,• 9
Visually check upon
receipt, and compare
against Mg-in-glass
thermometer
Upon recer.pt, visually
check and leak check
Visually check upon
receipt
Upon receipt, check with
suitable pressure gauge
Visually check upon
receipt
As above
Action if
requirements
are not met
Return to sup-
plier, and
note in pro-
curement log
As above
As above
As above
As above
As above
As above
As above
As above
(continued)
                                                        /frfr

-------
                                                               Section No.  3-14.1
                                                               Date July 1,  1986
                                                               Page 8
Table 1.1  (continued)
                                                                                   o
Apparatus/
supplies
                Acceptance criteria
                           Frequency and method
                               of measurement
                            Action if
                          requirements
                           are not met
Stopcock
  grease
                High vacuum high temper-
                ature chlorofluorocarbon
                grease
                           As above
                         As above
Barometer (or
 consult lo-
 cal weather
 station)
                Capable of reading atmos-
                pheric pressure to
                +2.5 mm Hg
                           Visually check;  cali-
                           brate against mercury-
                           in-glass barometer
                         As above
Storage bottle
                Polyethylene,  100-ml,  or
                greater capacity, screw
                cap
                           Visually check upon
                           receipt
                         Return to sup-
                         plier and note
                         in procurement
                         log
Wash bottle
                Polyethylene or glass
                           Visually check label
                           upon receipt
                         As above
                                                                                  O
Analytical
 balance
Capable of measuring
to +0.1 mg
Check with standard
weights upon receipt
and before each use
Replace or
return to man-
ufacturer
Volumetric
 cylinders
                50-ml (Class-A) with
                1-ml divisions
                           As above
                         As above
Ion Chroma-
 tograph
  1.  Columns
 (continued)
                1. Capable of giving
                nitrate ion peaks
                with baseline
                separation; capable of
                giving duplicate results
                within 5 percent of mean
                value
                           1. Check during
                           analyses
                         1. Consult op-
                         erator's manu-
                         al ;  regenerate
                         suppressor
                         column; clean
                         separator
                         column; check
                         performance
                         of components
                         below; replace
                         column(s) if
                         above actions
                         are unsuccess-
                         ful
                                                                                  O
                                                              /  ../ft/


-------
Table 1.1   (continued)
                                                              Section No. 3.14.1
                                                              Date July 1, 1986
                                                              Page 9
Apparatus/
supplies
Acceptance criteria
Frequency and method
    of measurement
  Action if
requirements
 are not met
2. Pump
3. Flow
    control
4.  Conduc-
    tivity
    detector
5. Recorder
2. Capable of delivering
eluent at constant and
repeatable flow rate
3. Capable of giving
repeatable indications
of eluent flow rate
4. Capable of giving
responses which can be
manually or electron-
ically integrated within
a precision of 5 percent
5. As above, if used to
record responses for
manual integration
2. Check during analyses
by monitoring flow rate
3. Check calibration
and repeatability upon
receipt
4. Calibrate according
to manufacturer's in-
structions prior to use
5. Check during
analyses
2. Consult oper-
ator's manual;
oil, clean, re-
repair, replace,
or return to man-
ufacturer; check
tubing of
ion chroma-
tograph for
leaks or ob-
structions;
check flow meter
performance
3. Consult oper-
ator's manual;
adjust, repair,
replace, or re-
turn to manu-
facturer;
check pump per-
formance

4. Consult opera-
tor 's manual;
Repair, replace,
or return to
manufacturer
5. Consult opera-
tor's manual;
adjust speed
Water
Meets ASTM D1193-82;
Type III
Check each lot, or
specify type when
ordering
Replace, or re-
turn to manu-
facturer
(continued)

-------
                                                               Section No.  3.14.1
                                                               Date July 1, 1986
                                                               Page 10
Table 1.1  (continued)
Apparatus/
supplies
Sulfuric
acid
Hydrogen
peroxide
Sodium nitrate
Sodium carbon-
ate
Sodium bicar-
bonate
p-Hydroxy-
benzoic acid
Acceptance criteria
Concentrated, ACS re-
agent grade
$0% aqueous solution,
ACS reagent grade
(store refrigerated)
ACS reagent grade
ACS reagent grade
ACS reagent grade
ACS reagent grade
Frequency and method
of measurement
As above
As above
As above
As above
As above
As above
Action if
requirements
are not met
As above
As above
As above
As above
As above
As above
o
                                                                                      o
                                                                                     o

-------
                                                   Section No. 3.14.2
                                                   Date July 1, 1986
                                                   Page 1
2.0  CALIBRATION OF APPARATUS
    Calibration of apparatus is one of  the  most important functions
in maintaining data quality.  It is highly recommended  that a labor-
atory log book of all calibrations be maintained.  Calibration proce-
dures  for  the  collection  flasks, field  barometer,  thermometers,
vacuum  gauge,  and analytical balance used in Method 7A are the same
as those  described  for  Method  7  (see  Section 3.6.2) and are not
duplicated  in  this  section; a form, however, for use in the analy-
tical  balance calibration is shown in Figure 2.1.  Detailed calibra-
tion procedures  for  the  ion  chromatograph system are described in
this  section.  Table 2.2 at the end of this section  summarizes  the
quality  assurance  activities  for  all calibrations  in  Method  7A
including those described in Section 3.6.2.

2.1  Ion Chromatograph System

    For  Method  7A,  the  calibration of the ion chromatograph  (1C)
system,  except  for  the initial  calibration  of  the  conductivity
detector, is conducted in conjunction  with  analysis  of  the  field
samples.   Specifically,  the  field samples are  analyzed  twice  in
between  three  analyses  of  the ion chromatograph calibration stan-
dards; the exact  sequence  is discussed in detail in Section 3.14.5.
The three analyses of the calibration standards are used to prepare a
calibration curve that is used to determine a calibration  factor for
calculating  the  concentration  of  nitrogen  oxides  in  the  field
 amples.  It is, however, highly recommended that the analyst conduct
  preliminary calibration of the 1C any time the system is set up for
analysis  of  NO   field  samples.  For this reason, the full discus-
sion of  the analysis of calibration standards and preparation of the
calibration curve is  presented  in  this section.  Also addressed in
this  section  are  preliminary considerations in  preparing  the  1C
system for use and other considerations for ensuring quality data.

2.1.1  Preliminary Considerations

    Conductivity  Detector - Prior to its initial use, the conductiv-
ity  detector of the ion chromatograph  must  be  calibrated  by  the
method described in the operator's manual.

    Recorder  -  A  strip chart recorder compatible with  the  output
voltage range of the conductivity detector  may be used to record the
ion chromatogram.  Manual measurement techniques that can be used for
quantitation of  the  chromatogram  include (a) peak height,  (b) peak
area by triangulation,  (c) peak area by multiplying peak height times
the peak width at half-height,  (d) peak  area by cutting out the peak
from the chromatogram and weighing it on an analytical  balance,  and
(e) peak area by planimetry.

    The use of an electronic integrator,  if available, is recommended
for greater accuracy and precision.   The electronic integrator can be
used in the peak area mode when the integration parameters are set up

-------
Balance name
                r
      Section No. 3.14.2
      Date July 1, 1986
      Page 2

Number    B//
Classification of standard weights
o
Date
/zs$r
0.5000 g
0. 5~5#
-------
                                                   Section No. 3.14.2
                                                   Date July 1, 1986
                                                   Page 3

properly.  The key integration parameters for peak area determination
concern the identification of the beginning and end of a peak and the
placement of the baseline under the peak,.  Analysts  should carefully
read the operator's manual and understand the selection and set up of
the  integration  parameters  for  their  particular integrator.  The
electronic  integrator  can  also  be  used in the peak  height  mode
provided that the peaks are symmetrical  and  an  acceptable standard
calibration  curve  can be generated without  any  calibration  point
deviating from  the line by more than 7 percent (see Subsection 2.1.3
of this section).

    Sample  Injection  Device  Contamination  Check - The analyst  is
encouraged to check the  sample injection device for contamination by
injecting  water  before  the  calibration  standards  are  analyzed.
Contaminants  will  appear  as  peaks  on the chromatogram.  Repeated
injections of water should be used to remove  contaminants  from  the
sample  injection  device.   If  certain peaks remain  after  several
injections of water then the water may be contaminated and should  be
replaced.

    Separation of Nitrate, NO3  - To ensure accurate results from the
ion chromatographic analysis, baseline  separation of the nitrate ion
(N03~)  peak from the other ion peaks should be achieved.  For_Method
7A, the separation of the N03~  peak from the sulfate ion (SO.") peak
is of major concern.  The S0.~ originates primarily from the sulfuric
acid  absorbing  reagent.  A second source of SO.  in a sample may be
sulfur dioxide present in the effluent stream sample.   Figures  2.2a
and 2.2b show two chromatograms, one having overlapping NO..,' and SO."
peaks, and the other having baseline separation of the NO3   and SO."
peaks.  The sulfuric acid concentration in the absorbing reagent used
for Method 7A is 10 times less than that for Method 7 to minimize the
problem of adequately separating N03~ from flO. .

    The  analyst is encouraged to check the performance  of  the  ion
chromatograph  system before analyzing samples  in  order  to  ensure
baseline  separation  of NOq~ is attainable.   A  test  for  baseline
separation of N03~ can  be  made  by  preparing  a  performance check
sample and analyzing during  the  recommended preliminary calibration
as follows:

    1. Pipet 10.0 ml of the 25 yg NO2/ml  working  standard  solution
into a 50-ml volumetric flask.

    2.   Into  the  same  volumetric  flask,  pipet 5 ml of absorbing
reagent.

    3.  Dilute with water to the mark.

    4.   Analyze  this  performance  check  sample  with  calibration
standards  in  the  same  manner  as described for field samples (see
Subsections 5.1.4,  2.1.2,  and 2.1.3).
                                                 !/*

-------
                                    Section No.  3.14.2
                                    Date July 1, 1986
                                    Page 4
                                             SO,
Figure 2.2a.  Example chromatogram having
              overlapping peaks.
 Figure 2.2b.  Example chromatogram showing
               baseline separations of peaks.
                                                         o
                                                         O
                                                         O

-------
                                                   Section No. 3.14.2
                                                   Date July 1, 1986
                                                   Page 5

    The  analyst  should check the chromatogram  of  the  performance
check sample for baseline  separation.  If the baseline separation is
marginal for the performance  check  sample and the samples have N0~
concentrations close to that of the highest standard  (5  yg N0~/ml7,
the  analyst   should   closely   monitor   subsequent  field  sample
chromatograms  to ensure that results are not adversely  affected  by
deterioration of the ion chromatograph column  or varying performance
of the ion chromatograph.

    The  final aspect of the performance check involves  a  precision
assessment.  The result  from  the  analysis of the performance check
sample should agree within 5 percent of the value for the 5 yg NO^/ml
calibration standard data point.

2.1.2  Preparation of Calibration Standards  - The preparation of the
calibration  standards  is perhaps the most critical  aspect  of  the
Method  7A analysis, since the quality of sample results will only be
as good as the quality of the calibration.  The steps observed in the
preparation of the calibration standards are detailed below.

    Stock Standard Solution

    1.   Dry approximately 5 g ACS-grade sodium nitrate  (NaNCU) in an
        oven at 105  to 110 C for  at  least  2  hours  prior to use.
        Drying  of the NaN03 is necessary to prevent NO  results from
        being biased high because of absorbed moisture.

    2.   Calibrate the analytical balance using a 2-g Class-S calibra-
        tion  weight  (see  Figure  2.1  for an example  form).   The
        balance reading should agree  within  2  mg  of  the  Class-S
        calibration  weight.  Corrective actions should be  taken  if
        this agreement is not achieved.

    3.   Allow the dried NaN03 to cool to room temperature in a desic-
        cator.    When  the  reagent  has cooled, weigh out 1.847 g to
        +0.002 g.   Cooling  is  required  to prevent weighing errors
        originating from convection  currents.   Storage of the NaNO«
        in the desiccator ensures that moisture will not be adsorbed;

    4.   Place weighed NaNO^ in a 1-liter Class-A volumetric flask and
        dissolve in exactly  1  liter  of  water.   Label  the  flask
        accordingly:                     '

                         NaNO3(aq)
                         StocR Standard
                         for EPA Method 7A
                         (1 mg NO,,/ml)
                         Date
                         Analyst's Initials

-------
                                                   Section No. 3.14.2
                                                   Date July 1, 1986
                                                   Page 6
o
         The solution is stable for one month  and should not be used
         beyond that time.  After about one month, there is increased
         risk that the reagent will be contaminated by microorganisms
         that feed on nitrate.  The use of such contaminated reagents
         will cause NO  results to be biased high.
                      X

    Working Standard Solution

    5.   Pour  about  25  ml of stock standard solution into a clean,
         dry beaker.

    6.   Using a 5-ml Class-A  pipet,  pipet  5  ml of stock standard
         solution into a 200-ml Class-A volumetric  flask.  Dilute to
         the calibration mark with water, and mix well.

         This solution is the Working  Standard;  its nitrate content
         represents  a  concentration  of  25 yg N02/ml.  The working
         standard  solution  is  prepared  fresh  for   each  set  of
         analyses.

    Calibration Standards

    7.   Prepare a series of five calibration standards by  pipetting
         1.0,  2.0, 4.0,  6.0, and 10.0 ml of working standard soluti
         (25  vjg/ml)  into  a series of five 50-ml Class-A volumetrif  J
         flasks.  The standard masses  will  equal,  25, 50, 100, 150/—/
         and 250 pg N02,  respectively. Dilute to the mark with either
         water or eluent solution, and mix well.

         The choice of diluent  is determined by practical considera-
         tions.  If the "water  dip"  (see Figure 2.2) is expected to
         interfere  with  the  nitrate peak of the chromatogram, then
         eluent  should  be used  as  the  diluent  since  this  will
         minimize the  "water dip."  Note: Whichever diluent is used,
         it is important  for the analyst to use. the same diluent for
         the field samples, the calibration standards, and the blank,
         as specified in the Federal Register.

2.1.3   Preparation and Validation of the Calibration Curve -  Method
7A specifies  the  determination of a calibration factor, S, which is
used to calculate the concentration of NO   in  the field samples.  S
is defined as the reciprocal of the slopexof the  calibration  curve,
which  is determined by preparing or calculating a linear  regression
plot of the standard  masses of the calibration standards (vg) versus
instrument response (peak height or area).  Determination  of  S does
not take into account the y-intercept, if present, of the calibration
curve.

    The  first subsection that follows describes the calibration pro-
cedures  and the determination of the calibration factor as specifie/"~"\
in Method 7A.   The  second subsection offers an alternative approach!   j
acceptable  to  the Administrator,  for  conducting  the  calibration—^

-------
                                                   Section No. 3.14.2
                                                   Date July 1, 1986
                                -                  Page 7

 calculations  that  utilize the non-zero y-intercept, if present.  This
 approach  is based  on  the calibration  procedures  of  Method  7D  and
 involves  the determination  of a calibration equation.  A data form
 which  can be  used  with both approaches is presented in Figure 2.3.

    Determination  of  the Calibration  Factor  (S) - The determination
 of the calibration factor,  S,  involves  the  three steps presented
 below.

    1.  Analyze each  of the calibration standards (25, 50, 100,  150,
 and 250  yg   NO,)  three times using the ion chromatograph.  Document
 chromatograms fsee   Subsection  5.1.4) and record the results on the
 analytical data form  for calibration standards (Figure 2.3).  Average
 the three responses for each of the five standards.

    2.  Use the average response for  the  five calibration standards
 to calculate  the  slope  of  the  calibration curve, graphically, by
 least  squares,  or by linear regression.   To  calculate  the  slope
 graphically,  plot  the instrument response (peak height or area count)
 on  the  y-axis against the corresponding N02 standard  concentration
 value  on the  x-axis.  Draw a "best-fit"  line  between the points and
 determine the slope of the line.  Least squares (a method  acceptable
 to the Administrator) can be  hand  calculated and is shown in Figure
 2.3.   To  calculate  the slope by  linear  regression,  use  the  N02
 standards as  the independent variable (x-axis)  and the corresponding
 instrument response as the dependent variable (y-axis).

    3.  The calibration factor, S, is calculated as the reciprocal of
 the slope of  the calibration  curve,  determined  from the "best-fit"
 line or the linear regression equation.  Any y-intercept is ignored.

    4.  The calibration factor, S, and  therefore,  the curve must be
validated.  Using the calibration  factor  for  calculation, the pre-
dicted sample mass for each calibration standard is compared with the
known  value  for that standard.  The predicted sample mass  must  not
deviate from  the known standard concentration  by  more than 7%.  The
quantity  "yg  N02  Predicted"  is  calculated  using the calibration
factor (S) and the detector response  (H), in millimeters or integra-
tor response,  as shown in Equation 2-1.


                                                         Equation 2-1
    yg N02    = S (yg/mm) x Detector (mm)
    Predicted              Response
                              H

The deviation of each predicted  sample  mass  from the known mass is
calculated using Equation 2-2.
                                                         Equation 2-2

    Deviation = yg NO2 Predicted - yg NO2 Standard x 1QQ%
      (%)                    yg N02 Standard
                                              V.	

-------
Plant

Date
          /
                                       Location

                                     1  Analyst
                                                             Section No. 3.14.2
                                                             Date July 1, 1986
                                                             Page 8
                                                                        o
 Was an integrator used?'	 yes
Was the intercept (I) used for calculat
ions? yes K no
Were all points within 7 percent of calculated value? S yes
Sample
Identifier
Std 1
Std 2
Std 3
Std 4
Std 5
Sample
Mass
(yg NOJ
25
50
100
150
250
Integrator Response
or Peak Height (mm)
H
1
O.I
/ZST*
2.$. 3
38- /
6>0.}
2
6.4-
ll't
1*3
39. /
527
3
62~
tf.0
zs-.r
30.^
5^.6,
Avg
' 6-25
72.66
ZfT.23
3^.00
5"f,6?
Predicted
Sample Mass
(yg N00)

52. //
/oz. i^
/r7./r
jL-f-3. ;r
no
Deviation
(*)
^/^6
/-^.23
^^.72-
1-4-.77
-^.5o
Predicted Sample Mass using Least Squares  to  Calculate Calibration Factor (S)
  with Zero Intercept
S - S1H1
       S2H2
                     S3H3
                                    S5H5
H
             H
                    H
    S =
   S =
              v g N02/mm
   Predicted Sample Mass (yg N0_)

    pg N0  = H x S = (6E3 )  x
                                                          Equation 2-1
Predicted Sample; Mass using Linear Regression  to  Calculate Calibration Factor (S)
  and Non-Zero Intercept (I)          '          --•           ,         "  '
    y = mx + b;  m =
                             b =
    x=i(y-b);i=S=
        m          m
    y = H;  and b = I (Intercept)  =

   Predicted Sample Mass  (yg NOp)

    yg N02  = S(H - I)

    pg N0_  at 25 yg standard = 	
                                                         Equation 2-4
        Figure 2.3-   Analytical data  form for analysis of calibration standards.
                                                                            .0

-------
                                 ji                  Section No. 3.14.2
                                                   Date July 1, 1986
                                                   Page 9

 This calculation is performed for each calibration standard using the
 average of the three response measurements.  If any point (known con-
 centration of standard) deviates from the line (predicted  concentra-
 tion)  by more than +7 percent, that standard should  be  remade  and
 reanalyzed.

    Linear regression using a hand-held calculator  is recommended to
 obtain the slope (and equation) for the calibration  curve.  Inexpen-
 sive calculators  are available which have linear regression programs
 that are quick and simple to use.  Graphical techniques are relative-
 ly simple matters when  all  the  calibration  data  points lie on or
 close to the line.  However,  when  deviations  from linearity occur,
 the  placement  of the "best-fit" line becomes ambiguous because  the
 data points are not evenly distributed.

    Determination  of  the  Calibration  Equation - As discussed pre-
 viously, Method 7A directs that the calibration factor, S, be used to
 calculate the field sample analytical results.   In  cases  where the
 calibration curve does not pass through the origin, the procedure  of
 Method  7A  could give biased results for both the field samples  and
 the linearity check since the equatiori for the calibration curve will
 contain an intercept term not taken into account in the calculations.
 Accordingly,  this section offers an alternative calibration approach
 adapted from  Method  7D.   The  approach involves determination of a
 calibration  equation  which takes into account both the slope of the
 calibration  curve  and  any  y-intercept  term  and which is used in
 calculating the NO  concentration of field samples.
                  A

    Derive  the linear calibration equation  or  curve  using  linear
 regression.   The  calibration  equation  should  be expressed in the
 following form:

          y = m x + b                                    Equation 2-3

where

         m = slope of the linear calibration curve, which is equal to
             the reciprocal of the calibration factor, 1/S, and

         b = y-intercept of linear calibration curve  which  will  be
             referred to as "I" for purposes of later calculations.

   As discussed in the previous section,  Method 7A requires that none
of the calibration data points deviate from the calibration  curve by
more than 7 percent  of  the  concentration at that point.  Method 7A
 (Section  5.2.3)   states   that  deviations  can  be  determined  by
multiplying  the  calibration factor S times the peak height response
for each  standard.    When the calibration equation with intercept is
used,  the quantity "yg N02 Predicted" is computed using the following
equation:

-------
                                                   Section No.  3.14.2
                                                   Date July 1,  1986
                                                   Page 10

   yg N02   = S (yg/mm) /Detector (mm) - I (mm)\          Equation 2-4
  Predicted             (  Response             I


As   before,  calculation  of  the  %  deviation  from  the  line  is
accomplished using Equation 2-2.  If any  deviation  is  greater than
7%,  the corresponding standard should be remade and reanalyzed.   If
this does  not  result  in  improved  results,  other  approaches are
discussed in the following subsection "Other Considerations."

2.1.4  Other Considerations - Method 7A requires that if any calibra-
tion standard  point  deviates from the standard calibration curve by
more than 7%, then that corresponding calibration standard is  to  be
remade and reanalyzed.  This corrective action may not always  reduce
the calibration point deviations below 7%.  Some potential causes for
deviation  of  the  calibration  points  from  the calibration  curve
include (a) improper pipetting procedures used to prepare calibration
standards, (b) improper technique for manual  sample  Injection  into
the  ion  chromatograph,  (c)  inaccurate  measurement   of  the  ion
chromatograph response, and (d) non-linear  detector response.   Table
2.1 shows the precisions for calibration operations for Method 7A.


                  TABLE 2.1.  TARGET PRECISIONS FOR
                 CALIBRATION OPERATIONS OF METHOD 7A
                                                                     O
   	Operation	Precision Target (%)

    Pipetting                                    1

    Introduction of Samples                     <1
       into Ion Chromatograph

    Measurement Response
       o Peak Height                            1-4
       o Triangulation                           4
       o Height X Width at
           Half-Height                           3
       o Electronic Integration                <0.5
    Pipetting  Procedure  and Pipetting Errors  -  In  preparing  the
calibration standards,  pipetting is the most critical step.  Serious
errors  can  originate from poor pipetting  technique.   In  general,
errors will appear as high biased NO  results.  The correct pipetting
procedure is described below.
                                                                     o

-------
                                                   Section No. 3.14.2
                                                   Date July 1, 1986
                                                   Page 11

    The  pipet should be inspected before use and checked  to  ensure
that the tip is not chipped.   The pipet should be replaced if a chip
is observed.

    The pipet should be rinsed  with  the  reagent to be pipetted and
checked for cleanliness before use as follows.  Approximately 2 ml of
reagent is drawn into  the pipet, which is then rotated and tilted in
order to expose the inner  surface  to the solution.  The rinse solu-
tion is then allowed to drain freely  from  the  pipet  into a beaker
assigned for waste.  If the pipet is clean,  the analyst will observe,
after about 10 seconds, that all the rinse solution will have drained
from the pipet with the exception of a  small  quantity  remaining in
the  tip.   If  this  is  not  observed, either the pipet  should  be
cleaned, or another pipet should be obtained.   The  rinse  and check
for cleanliness should be performed at least once.

    For the actual pipetting, reagent  is  drawn into the pipet until
the liquid meniscus is above the calibration mark.  The pipet is then
withdrawn from the solution and the end  is  wiped  with a laboratory
tissue.  Next, the pipet is brought to  a  vertical  position and its
tip  is brought to touch the inside of the beaker assigned for waste.
The liquid  in  the  pipet  is then allowed to drain slowly until the
meniscus coincides with the calibration mark.

    The pipet is then transferred to  the  appropriate container and,
with the pipet in a vertical position and its tip touching the inside
wall of the container, the liquid is allowed to drain freely into the
container.  The pipet's tip should be kept  in  contact with the wall
for  roughly 10 seconds after the liquid has apparently drained.  The
pipet is then removed from the container without disturbing the small
amount of liquid remaining in the tip.

    It is important to recognize that  Class-A  pipets are calibrated
in a manner  which  accounts  for  the  drainage  time and the liquid
remaining in the tip.   If  dirty  pipets  are  used or if the proper
draining  technique is not observed, NO  results will be biased high.
Low biases will occur  if  the  liquid  remaining in the pipet tip is
blown  out  into  the receiving container.  The significance of these
biases depends on the size of the  pipet  involved.  For example, the
error with a dirty 25-ml pipet may be  undetectable,  while the error
for a 1-ml pipet can easily exceed 10 percent.

    The precision of the pipetting operation can be checked gravimet-
rically using water.  The technique involves pipetting a known volume
of water into a tared  container  and  determining  the weight of the
water.  The precision  of  the  pipetting operation is estimated from
the results of several repetitions.

    The procedure for manually injecting a sample into the ion chrom-
atograph can be a source  of  error  when analyzing calibration stan-
dards, field samples,  and  QA  samples.   For  fixed  loop injection
systems, considerable variation can result  from injecting the sample

-------
                                                   Section No.  3.14.2
                                                   Date July 1,  1986
                                                   Page 12

into  the  loop too fast, resulting in  the  sample  loop  not  being
completely filled.  A slow,  deliberate  injection of the sample into
the  loop  will  completely  fill  the  loop.  The precision  of  the
injection procedure can be checked by performing repetitive  analyses
on a single sample.

    Chromatogram  Quantitation  -  The choice of quantitation methods
for the ion chromatograms can also be a source  of  error when analy-
zing calibration standards,  field samples, and QA samples.  As shown
in Table  2.1, measurement of the detector response by manual methods
has a higher degree  of  imprecision compared to measurement by elec-
tronic  integration.   Method  7A states that peak height measurement
can be used provided  the  peaks  are symmetrical and the required 7%
deviation of calibration points from the standard  calibration curves
can be met.  The peak  height measurement method, even with symmetri-
cal peaks, may not produce a linear standard caliration curve because
the  peak width of the higher concentration standards will  typically
be wider than  the  peak  width of the lower concentration standards.
Figure 2.4 shows the difference  in  the  linearity  of ion chromato-
graphic  calibration  curves  using  the peak area mode and the  peak
height mode.   The  dead  volume  of  the  ion  chromatograph system,
particularly suppressed ion chromatograph systems,  can  also  affect
the peak width.  Quantitation by peak area measurement will eliminate
the   biases  caused  by  widening  peaks  provided  the  peak   area
measurement is done properly.  The use of an electronic integrator in—,^^
the peak area mode for ion chromatograms  with baseline separation c[   )
the nitrate peak will produce the most precise calibration curves anV^x
subsequent accurate analyses of field samples and QA samples.
                                                                  o

-------
Response
                                                Section No. 3.14.2
                                                Date July 1, 1986
                                                Page 13
                        Peak Area
                        Approach
                                                X>
                                  Peak  Height
                                  Approach
 1OO
ug N
         150
                                       Z.OO     2.50
        Figure 2.4,
Linear and non-linear ion chroma
tographic calibration curves.

-------
                                                              Section No.  3.14.2
                                                              Date July 1,  1986
                                                              Page 14
               TABLE 2.2.  ACTIVITY MATRIX FOR CALIBRATION OF EQUIPMENT
                                                                                  o
Apparatus
Acceptance limits
Frequency and method
    of measurement
  Action if
requirements
 are not met
Collection
  flask
Measure volume within
10 ml
On receipt, measure with
graduated cylinder
Recalibrate
Barometer
Reading agrees within
2.5 mm (0.1 in.) Hg of
mercury-in-glass
barometer
Upon receipt and before
each field test
Repair
or return
Thermometer
Reading agrees within
1°C (2DF) of mercury-
in-glass thermometer
As above
As above
Vacuum gauge
  (mechanical
  only)
Reading agrees within
2.5 mm (0.1 in.) Hg
of mercury U-tube mano-
meter
As above
As above
Analytical
  balance
Weight within 2 mg of
standard weights
(Class S)
Use standard weight
before preparation of
working solution
Repair or
return to
manufacturer
O
Ion chroma-
  tograph
Calibration curve should
be linear; data points
for calibration stan-
dards must not deviate
from the linear calibra-
tion curve by more than
+7 percent
With each set of field
samples; calibration
standards prepared from
sodium nitrate
Interpret data
using another
technique: e.g.,
if using peak
height, change
to peak area;
conduct addi-
tional analy-
ses of cali-
bration stan-
dards; cali-
brate conduc-
tivity detec-
tor; consult
operator's
manual
                                                                                O

-------
                                                   Section No. 3.14.3
                                                   Date July 1, 1986
                                                   Page 1
3.0  PRESAMPLING OPERATIONS
    This section addresses  the  preparation  and packing of supplies
and equipment needed for the sampling.  The pretest  preparation form
(Figure 3.1) can be used as an equipment checklist.  Many presampling
operations for Method  7A  are identical to those for Method 7.  This
section will only discuss  the operations that are different; however
all quality assurance activities for Method 7A presampling operations
are  summarized in Table 3.1 at the end  of  this  section  including
those  described in Section 3.6.3.  See Section 3.0 of this  Handbook
for details on preliminary site visits.

3.1  Apparatus Check and Calibration

    Previously used equipment should be  visually  checked for damage
and/or excessive  wear  before  each  field  test.   Items  should be
repaired  or replaced (as applicable) if judged to be unsuitable  for
use.  A pretest  sampling  checks form (Figure 3.1) summarizes equip-
ment calibration.   The pretest preparations form (Figure 3.2) can be
used as an equipment check  and  packing  list.   The  completed form
should be dated, signed by  the  field  crew supervisor, and filed in
the operational log book.  The replacement  of  worn or damaged items
of equipment should  be  initiated.   Procedures  for  performing the
checks are given herein; a check is placed  in  the  proper  row  and
column  as the check/operation is completed.  Each team will have  to
construct its own checklist according to the  type  of sampling train
and equipment it uses.

3.2  Reagents

    Unless otherwise indicated,  it  is  intended  that  all reagents
conform  to  the  specifications  establishod  by  the  Committee  on
Analytical Reagents of the  American  Chemical  Society  (ACS), where
such specifications  are available; otherwise, use the best available
grade.  See Subsection 1.2.3 of Section 3.14.1 for  water  specifica-
tions .

3.2.1   Sampling - The absorbing reagent is prepared by adding 2.8 ml
of concentrated sulfuric acid (H2SO.)  to  a  100-ml flask containing
water  and  diluting to volume  witn  mixing.   Add  10  ml  of  this
solution,   along  with  6  ml of 3% hydrogen peroxide (H202) that has
been  freshly  prepared  from  a 30 percent solution,  to  a  1-liter
flask.   Dilute  to  volume  with water,  and mix well.  Prepare fresh
absorbing solution weekly,  and avoid exposure  to  extreme heat or to
direct  sunlight,   as  these  will  cause  the hydrogen  peroxide  to
decompose.   If the reagent  must  be  shipped  to  the  field,   it is
advisable that the absorbing reagent be prepared fresh on-site.

3.2.2   Analysis - The following reagents are needed for analysis and
standardization:

-------
                                               Section  No.  3.14.3
                                               Date July 1,  1986
                                               Page 2
                                                                o
Date    t- 2,5 f&S	 Calibrated by _

Flask Volume
Flask volume measured with valves?     ^ 	 yes 	 no
Volume measured within 10 ml of actual volume?*  
-------
                                             Section No. 3.14.3
                                             Date July 1, 1986
                                             Page 3


Apparatus check
Probe
Glass liner
clean
Heated properly*
Leak checked
Collection Flask
Clean
Leak checked
Temperature
gauge
Evacuation System
Leak- free pumps
Manifold and
tubing
U-tube manometer
Barometer
Reagents
Water
Absorbing solu-
tion*
Sample Recovery
Dropper or burette
Sample bottles
Pipette, 25 ml

Acceptable
Yes

x
^
X
X

x"
X



X
X
X
cX

x'
^


X
X
^
NO
























Quantity
required

3



/4
T




2
3
2-
/

/ ///cr
(
/ ///^~

2
14-
' i

Ready
Yes

X



X'





IS^
X
X
X

X

X

^
^r
^x^
No























Loaded
and packed
Yes

^x""



ls^





^
X
X
X"

x
ys"


^
X
^
No























*Most significant items/parameters to be checked.
             Figure 3.2.    Pretest preparations.

-------
                                                   Section No.  3.14.3
                                                   Date July 1,  1986
                                                   Page 4

    Stock  standard  solution  - Dissolve exactly 1.847  g  of  dried
sodium nitrate (NaN03)[or 2.198 g of dried potassium nitrate (KN03)]
in  water,  and dilute to 1 liter in a volumetric  flask;  mix  well.
Prepare fresh after 1 month.

    Working standard solution -  Dilute 5 ml of the standard solution
to 200 ml with water in a volumetric flask, and mix well.   Note;  One
ml  of  the working standard  solution  is  equivalent  to  25g  of
nitrogen dioxide.

    Eluent solution - Weigh  1.018 g  of sodium carbonate (NaCOo)  and
1.008 g of sodiumbicarbonate  (NaHCCU), and dissolve in 4 liters of
water.  Other eluents may be used (see Subsection 1.4.3).
o
                                                                     o
                                                                    o
                                                 I?'
                                                     L

-------
                                                               Section No. 3-14.3
                                                               Date July 1, 1986
                                                               Page 5
               TABLE 3.1.  ACTIVITY MATRIX FOR PRESAMPLING PREPARATION
Characteristic
Acceptance limits
Frequency and method
    of measurement
  Action if
requirements
 are not met
Apparatus Check

Probe
1. Clean; glass liner
inert to oxides of
nitrogen

2. Heating properly if
equipped with heating
system

3. Leak free
1.  Before each test
                                           2.  As above
                                           3.  Pressure <380 mm
                                           (15 in.) Hg
Replace
                          Replace or
                          repair
                          Replace or
                          repair
Collection
  flask
Clean; volume within
10 ml
Before each test,
clean with strong de-
tergent and hot tap
water, and rinse with
tap water and then
ASTM Type III water;
periodically clean
with grease remover
Repeat cleans-
ing of flask
and/or meas-
ure volume
Evacuation
  system
Vacuum of 75 n™
(3 in.) Hg absolute
pressure in each flask;
leakage rate <10 mm
(0.4 in.) Hg/min
Before each test, check
for leaks using Hg-
filled U-tube manometer
Correct leaks
Absorbing
Reagent

Sulfuric acid
  concentrated
Final concentration:
0.28 ml/liter
Prepare fresh absorbing
solution weekly; use
graduated pipette
Make up new
solution
Hydrogen perox-
  ide, 3%
6 ml/liter
Water
Deionized distilled
to ASTM specifications
D 1193-82, Type III
                          Prepare fresh
                          for each anal-
                          ysis period
(continued)

-------
                                                                Section No.  3-14.3
                                                                Date July 1,  1986
                                                                Page 6
TABLE 3.1.  (continued)
                                                               D
Characteristic
Acceptance limits
Frequency and method
    of measurement
  Action if
requirements
 are not met
Analytical
Reagents

Stock standard
  solution
1. 1.8V7 +0.001 g
NaNOo ACS reagent
grade into a 1-liter
volumetric flask
(Class-A)

2. Stored for less
than 1 month
1. On makeup of solution
  use analytical balance
                                           2. Date solution
1. Make up new
  solution
                          2. As above
Working standard
  solution
5 ml of stock solution
into 200-ml volumetric
flask (Class-A)
On makeup of solution,
use Class A pipet and
proper technique
As above
Eluent solution
1.018 g + 0.001 g of
NaCO, and 1.008 g
+ 0.002 g of NaHCO-
in 4 liters       •*
On makeup of solution,
  use analytical balance
As above
                                                                                  o
Packing Equip-
ment for Ship-
ment

Probe
Rigid container lined
with polyethylene foam
Prior to each shipment
Repack
Collection
  flasks and
  valves
Rigid container lined
with polyethylene foam
As above
As above
Evacuation
  system, tem-
  perature
  gauges,
  vacuum lines,
  and reagents
Sturdy case lined with
polyethylene foam
As above
As above
Evacuation
  pump
Shipping container
or housing designed
for travel
As above
As above
                                                                                 O

-------
                                                   Section No. 3.14.4
                                                   Date July 1, 1986
                                                   Page 1
4.0  ON-SITE MEASUREMENTS
    The bn-site activities include transporting equipment to the test
site, unpacking and assembling  the  equipment, confirming duct meas-
urements  and  traverse  points  (if  volumetric  flow  rate is to be
determined),  determining  the  molecular  weight  of  the stack gas,
sampling  for  oxides  of  nitrogen,  and  recording the data.  These
activities are the  same  as  for  Method 7 (Section 3.6.4), with the
exception of a portion of the sample recovery procedures as described
below.  Blank  data  forms  can  be found in Section  3.14.12 for the
convenience  ..of  the  Handbook user.  Table 4.1 at the  end  of  this
section  summarizes  the quality assurance activities relative to all
on-site  measurements  in  Method  7A,  including those described  in
Section 3.6.12.

4.1  Sampling

    On-site sampling procedures for Method  7A  are the same as those
for  Method 7.  See Subsection 4.3  of  Section  3.6.4  for  detailed
descriptions of sampling  procedures.   For  convenience, examples of
completed field data  forms  for  Method  7  are  reproduced  in this
section (Figures 4.1A and 4.IB); blank copies are provided in Section
3.14.12.

4.2  Sample Recovery

    Sample recovery procedures should  be  performed as described for
Method 7 (Section 3.6.4),  with  the  exception  that  the  steps for
checking  and  adjusting the pH of the sample should be deleted (note
changes in Figures 4.2A, 4.2B, and 4.3).

    A 16-hour minimum  sample  absorption  period  is  required as ±n
Method 7.   Samples should be recovered within 4 days of collection.
As currently written,   the  method  states that the samples should be
stored no more.than 4 days between collection and analysis.  However,
a recent study   utilizing samples from nitric acid  plants and power
plants  indicates  that  the  storage  period - between  recovery  and
collection may be extended to 30 days.

-------
   Plant
   Sample location

   Operator
                           QuHt-i,   &0 '/•€!-
City

Date
Barometric  pressure (P,   )
                                                                                            . 84-
                                                                                                          in.  Hg


Sample
number
M-l
M-Z


Sample
point
location
6-11
L>~ '/O
C-10

Sample
time
24-hr
0733
0745"


Probe
temperature ,
°F
-2-10
2-/0


Flask
and valve
number
£-/3.
££ -10

Volume
of flask
and valve (Vp) ,
ml
2.6/3
ZolO

Initial pressure
in. Hg

Leg A±
73.6
/3.7
73.7

Leg Bi
/3.7
/3.8
737

pia
Z-5-f-
z.3f


Initial temperature

°F(ti)
73
73


°R(Ti)b
^53
5-33

Px = pbar
Ti = fci + 46° F*
  O
                             Figure 4.1A.  Nitrogen oxide field  data  form (English units).
                                                       O
                                                                                                                •DOW
                                                                                                                C> ta  0> rt
                                                                                                                     K
                                                                                                                M Q O
                                                                                                                   CD
                                                                                                                     O
                                                                                                                  H* •

                                                                                                                     CO

                                                                                                                  lO h-1
                                                                                                                  03 it*
                                                   O

-------
Plant frc-frvL rower r
Sample location &SS* 0U-/-L
Operator &£>O

l^»+ city C^=flJ^*>^ , /SavT&r><±
'ff- , 250/fer fcl Date Z /E-7 /^ <5T
Barometric pressure (P, ) 7O(p



, 2— mm Hg



Sample
number
M-l
M'Z
A?~3

Sample
point
location
a- it
&-10
c-io

Sample
time
24-hr
0733
074-5-
00oi

Probe
temperature ,
°C
/OO
loo
loo

Flask
and valve
number
££r&
&£'/&
££-%
Volume
of flask
and valve (V.,).
ml
2013.
ZO/0
200®
Initial pressure
in. Hg


Le.g A±
372
373
37Z5-

Leg B±
371
370. $~
370

*ia
17.2.
Jb.7
n.7

Initial temperature


°C (t±)
13..2
ZI.Z.
^3.r

^'(Ti)1*-
2fs: z
2-74 Z
Z'ft.S'
Pi
273°C.
                                                                                                                    »« O CO
                                                                                                                    Qj 0) (D
                                                                                                                   tQ tt Q
                                                                                                                    (D (D rt-
                                                                                                                        H-
                                                                                                                    (*>Q O
                                                                                                                      C 3
                               Figure  4.1B.  Nitrogen  oxide field  data form (metric  units).
                                                                                                                        00
                                                                                                                      vo
                                                                                                                      03
                                                                                                                      o\

-------
                 Plant
                                                          Date
     Sample recovery personnel cj?.     £i&r    Barometric pressure, (P,   )

     Person with direct responsibility for recovered samples   /y.
                                                                                                  in.  Hg


Sample
number
A/7-/
/L/2--7
ni £~
Final pressure,
in. Hg

Leg Af
/•(/
/ 9
2.0

Leg Bf
0-6
ft 9)


pfa
17. W
T ~1 QA.


Final temperature,

°F (tf)
73
72-
73

°R (Tf)b
^"33
5^3 Z

Sample
recovery
time,
24-h
/3ZZ
IB4-0
/f/s"

Liquid
level
marked
^
^

Samples
stored
in locked
container
^
^^

Pf - pbar
                                                     460°F-
Lab person with direct responsibility for recovered samples

Date recovered samples received   3/1 /Po .    Analyst   ^".

All samples identifiable?

Remarks
                              Uf
                                            fS
All liquids at marked level?   ^BS
                                                                                     I
             Signature of lab sample  trustee
      •D O W
      W 0) CD
      tQ rt- O
      CD CD rf
          H-
      rf^ U O
O
                Figure 4.2A.   NO   sample  recovery  and integrity data form  (English units).
                                        O
                                                                                                    vD
                                                                                                    03
O

-------
                         Plant
                                                                  Date
Sample recovery personnel  (y.
                                                                  Barometric pressure, £/•        i£— Ui


Lab person with direct responsibility  for  recovered samples


Date recovered samples received    ^///uo    Analyst  &.


All samples identifiable? 	


Remarks
                                                             All  liquids at marked level?
                     Signature of lab sample trustee
                                    T.
                        Figure 4.2B.
                   sample recovery and integrity data form (metric units)
                                                                                             •a a w
                                                                                             cu o> CD
                                                                                             IQ tt O
                                                                                             (D 0) d-
                                                                                                 I-1-
                                                                                             01 Ci O
                                                                                               C D
                                                                                                     O
                                                                                                   H1 •
                                                                                                   N

                                                                                                     W



                                                                                                   CD »>

-------
                                               Section No. 3.14.4
                                               Date July 1, 1986
                                               Page 6
Sampling   ,
Volume of 25 ml of absorbing solution** placed in flask?
Flask valve stopper in purge position?
Sampling train properly assembled?
  Leak free?* 	\/      Stopcock grease used?
  Type? 	£
Flask evacuated to 75 mm (3 in. ) Hg pressure?
  Leakage from manometer observation?* _ #, /
  [e.g., maximum change in manometer of £ 10 mm (0.4 in.)
  Hg/min]	
Initial pressure of flask recorded?* 	__,_	
Initial temperature of flask recorded?*	
Probe purged before sampling? 	S
Sample collected properly?* 	
-------
                                                                Section No. 3.14.
                                                                Date July 1, 1986
                                                                Page 7
                Table 4.1.  ACTIVITY MATRIX FOR ON-SITE MEASUREMENTS
Characteristic
Acceptance limits
Frequency and method
    of measurement
  Action if
requirements
 are not met
Apparatus
 assembly
Assemble using Fig.
1.1; no leakage
Before sample collec-
tion, visually and
physically inspect all
connections
Check for
leaks; repair
system;
repeat test
Operational
 check
Maximum vacuum of
75 mm (3 in.) Hg
absolute pressure
                   Leakage rate £10 mm
                   (0.4 in.) Hg/min
Before sample collec-
tion, use Hg-filled
U-tube manometer
                        As above
Check system
for leaks;
check vacuum
pump

Check all
joints and
valves for
source of leak
Sample
 recovery
Shake flask for 5 min

Let flask set for a
minimum of 16 h, but
no more than 4 days
                   Shake flask for 2 min

                   Determine flask pres-
                   sure and temperature

                   Mark sample level on
                   container

                   Record data on data
                   form (Fig.  4.2)
                                           During each sample
                                           collection, use mano-
                                           meter and Celsius
                                           thermometer
                          Reject sample,
                          rerun test
Sample logistics
Properly label all
containers, etc.

Record all data on
field data forms
Visually check each
sample

As above
Complete the
labeling

Complete the
data records
                                                        ill-

-------
o
o
o

-------
                                                   Section No. 3.14.5
                                                   Date July 1, 1986
                                                   Page 1
 5.0  POSTSAMPLING OPERATIONS
    The postsampling operations include  checks  oh (a)' the apparatus
used  in  the  field to quantify sample volumes (volume, temperature,
and pressure measurements), and (b) analyses of the samples collected
and forwarded to the base laboratory.  If the laboratory receives the
samples in the sample flasks, laboratory personnel will  have to com-
plete the sample recovery procedures referred to in Section 3.6.4.

    The  postsampling  checks on the sample collection train are  the
same as for Method 7 (Section 3.6.5).  The analytical  procedures for
Method  7A  are  different from Method 7  and  are  discussed  below.
Figure 5.1 is a checklist for  all  Method  7A  posttest  operations.
Table 5.1 at the end of this section summarizes the quality assurance
activities  for  all  postsampling operations for Method 7A including
those described in Section 3.6.5.

5.1  Analysis (Base Laboratory)                               •• <,,,-.

    Calibration  of  the ion chromatograph, including preparation  of
the calibration standards and preparation of the field  samples is of
primary importance to a precise  and  accurate  analysis.  For Method
7A, the calibration of the 1C is conducted in conjunction with analy-
sis  of  the  field  samples  (and quality assurance samples).   This
section  presents  the  steps  for  analysis  of  the  field  samples
including preparation of samples, field blanks,  and  use  of quality
assurance samples.  The relationship  between  analysis  of the field
samples and  preparation  of  the  calibration  curve  is  addressed.
However, because a  calibration and performance check of the 1C prior
to conducting any NO  analyses is highly  recommended,  the  detailed
discussion  of  the $C calibration is presented  in  Section  3.14.2.
Therefore, the analyst should  use Section 3.14.2 in association with
this section (3.14.5) in conducting the analysis.  In particular, the
analyst  is encouraged to review the discussion of  pipetting  errors
(see  Subsection  2.1.4).   Upon  completion  of  each  step  of  the
preparation of the calibration curve and of each sample analysis, the
data should be entered on the proper data form.

5.1.1  Preparation of Field Samples - Check the  level  of the liquid
in  the  sample  container  and  confirm  whether any sample was lost
during shipment;  note this  on  a  data  form  such  as that shown in
Figure 5.1.   If  a  noticeable amount of leakage has occurred, either
void  the  sample  or  use  methods  subject  to the approval of  the
Administrator  to correct  the  final  results.   Immediately  before
analysis  prepare  each  field  sample.   The  following steps detail
sample preparation operations.

    1.   With the aid of a funnel, transfer  the contents of the samp-
        ling flask to a 50-ml Class-A volumetric flask.

    2.   Add approximately  a  5-ml  portion  of water to the sampling
        flask,   replace the stopcock (ensuring  that  it  is  in  the

-------
                                               Section No.  3.14.5
                                               Date July 1,  1986
                                               Page 2
                                                                  o
Reagents
Sodium nitrate dried at 105° to 110°C for a minimum of
  2 hours before use?
Stock standard solution (sodium nitrate) less than 1 month old?
Sample Preparation
Has liquid level noticeably changed?* 	/Vp	
  Original volume 	  Corrected volume

Analysis
Standard calibration curve prepared?* 	*
All calibration points within 7 percent of linear calibration
  curve?*
Reagent blanks made from absorbing solution? _ .X
Same injection volume for both standards and samples? _ */_
Duplicate sample values agree within 5 percent of their mean?
O
All analytical data recorded on checklist and laboratory form?
* Most significant items/parameters to be checked.
                Figure 5.1.   Posttest operations.
                                                                 O

-------
                                                   Section No. 3.14.5
                                                   Date July  1,  1986
                                                   Page 3

       closed  position),  and rinse  the  interior  by  shaking and
       rotating  the  flask.   Transfer  the rinse to the  volumetric
       flask.  Repeat the rinse with another  5-ml  portion of water,
       and add this rinse to the volumetric flask also.

    3. Reassemble the sampling  flask  and  place the stopcock in the
       closed  position to prevent contamination during storage  prior
       to reuse.

    4. Using water, dilute the contents  of  the  volumetric  flask to
       the mark.  Mix the contents of the flask well.

    5. Using a 5-ml Class-A pipet, pipet a 5-ml aliquot of the sample
       into another 50-ml  Class-A volumetric flask.  This aliquot is
       diluted to the mark with either water or eluent solution.  Mix
       the contents of the flask well.

    The diluent used must be the same  as  that used for the  calibra-
tion standards.  (See Subsection  2.1.2  Preparation -of  Calibration
Standards.)                           ,

5.1.2   Preparation  of Reagent Blank - The reagent blank is  prepared
in essentially the same manner  as the field samples.  The difference
in  procedure  occurs  at  the  first step.  In preparing the reagent
blank, 25 ml of absorbing  reagent  is transferred to a 50-ml Class-A
volumetric  flask.   A  25-ml  pipet  may  be used for measuring and
dispensing the reagent solution; however,  the  use  of  a  graduated
cylinder  will  give  results of acceptable accuracy  and  precision.
After introducing the absorbing reagent  into  the  volumetric flask,
add  water  to the mark, and mix the contents of the flask well.  The
remaining steps for preparing the  reagent  blank,  are*; identical., to
those of Step 5 under Preparation of Field Samples^  ~V    .-••*• : t  r';,r-
                      ' -— --- —'~  "	   ~~"~—~" -   • \~   * "" * —"•'—~~- ~-  "           *^  ^

    The reagent blank is used to adjust the analytical results of the
field samples for matrix effects of the  absorbing  reagent   and the
water.   (The  sample  matrix is simply the medium that contains the
substance  to  be analyzed, which in this case is nitrate.)   Because
ion chromatography involves separation of the ions prior to detection
and quantification, the potential for the sample matrix  to interfere
with the analysis is small.  For Method 7A,  matrix effects can  arise
from the  presence of (a) nitrate contaminant in either the absorbing
reagent  or the water, or (b) a contaminating substance appearing  on
the  chromatogram  at  about the same time as the nitrate  peak.   In
practice, the ion chromatogram should exhibit no significant  response
at that point where  nitrate should appear.  Nevertheless, since data
are adjusted  for  the reagent blank,  quality results can be  obtained
even  if  contamination   exists.   The  presence  of  contamination,
however,  indicates the need for greater quality control in connection
with reagent integrity.
                            Audit Samples - The quality of analytical
                                                            solutions
5.1.3   Quality  Assurance	
results  can  be assessed by  analyzing  nitrate  standard
                                                 (I
                                                   11!

-------
                                                   Section No.  3.14.5
                                                   Date July 1,  1986
                                                   Page 4

prepared  by an independent laboratory.  For such standard solutions,t   )
or quality assurance  audit  samples, the concentrations are known to ^-^
the control agency (the auditor) but are unknown to the analyst.

    Subsection 3.3.5 of the Federal Register  promulgation  of Method
7A (see Section 3.14.10) requires the analysis of  quality  assurance
audit samples  as described in Method 7.  This means that when Method
7A is used to demonstrate  compliance  with an EPA pollutant emission
standard (specified in 40 CFR Part 60),  a  performance audit must be
conducted  on the analytical phase of the method.  Nitrate samples in
glass vials must be obtained  for  this  performance  audit  from the
Quality  Assurance  Management Office at each EPA Regional Office  or
from  the  responsible  enforcement agency.  The addresses of the EPA
Regional Quality Assurance Coordinators  are  shown  in  Table 5.1 of
Section 3.0.5 of this Handbook.

    The  concentration of each audit sample measured by  the  analyst
must  agree  within  10 percent (relative error) of the actual  audit
concentration.   The relative error is calculated using the following
equation:
                                                         Equation 5-1

                   RE « Cd " Ca x 100
                          Ca

where                                                               /*~N

         C, = Determined audit sample concentration, mg/dscm, and

         C  = Actual audit sample concentration, mg/dscm.
          a


5.1.4   Analysis  of  Calibration  Standards,  Reagent  Blank,  Field
Samples,  and  Quality  Assurance Samples - Field samples  should  be
recovered  within  4  days  of  sample  collection.     As  currently
written, the method states that the samples should  be stored no more
than 4- days between  collection and  analysis.   However,   a recent
study   utilizing samples from nitric acid  plants  and  power plants
indicates that the storage period between recovery and collection may
be  extended  to 30 days.  Sample analysis using an ion chromatograph
is a straightforward  operation provided that the instrument has been
properly  set  up  (see Section 3.14.2).   All  samples  (calibration
standards,   reagent  blank,  field  samples,  and  quality  assurance
samples)  should be introduced into the ion chromatograph  using  the
same procedure.   Sample  introduction  involves  filling  a constant
volume  sample  loop  using  a syringe or automatic sampling  device.
Sample  loops  give extremely repeatable injection volumes;  however,
the volumes that identify sample  loop  capacity  are not necessarily
accurate.  Nevertheless, accurate results  can  be  obtained  without
having  accurately  known sample loop volumes, provided that the same
sample  loop  is  used  for injecting field samples  and  calibration
standards.    With  this  procedure,  any  inaccuracy in the injectio/"~\
volume is accounted for by the calibration.                         (   )

-------
             . ;                                     Section No. 3.14.5
                                                   Date July 1, 1986
                                                   Page 5

    Ion chromatographic  analysis  of  calibration  standards,  field
samples,  reagent blank, and quality assurance samples are  performed
in five phases during the same day,  alternating between the calibra-
tion standards and unknown  samples  to  account for instrument cali-
bration  drift.  These phases are shown in the schedule below.   When
Method 7A is used to demonstrate compliance  with  an  EPA  pollutant
emission  standard, the quality assurance audit samples described  in
Subsection 5.1.3 must be analyzed with the field samples.

         Phase                      Activity

          1         First analysis of all calibration standards.

          2         First  analysis  of all  field  samples,  reagent
                    blank,   and   quality   assurance  samples,   if
                    applicable.

          3         Second analysis of all calibration standards.

          4         Second analysis of  field samples, reagent blank,
                    and quality assurance samples, if applicable.

          5         Third analysis of all calibration standards.

    The calibration standards are analyzed  in  triplicate; the field
samples, reagent blank, and quality assurance samples  in  duplicate.
Replication of analyses  increases  the accuracy and precision of the
results.  Each chromatogram  obtained  from  the  analysis  should be
documented with the following information:


    o   sample identification,

    o   injection point,

    o   injection volume,

    o   nitrate retention time,

    o   sulfate retention time,

    o   eluent flow rate,
    o   detector sensitivity setting, and

    c   recorder chart speed.


Figure 5.2 shows an  example  chromatogram having acceptable documen-
tation.  The injection volume, eluent flow rate, detector sensitivity
setting, and the recorder chart speed need to be documented only once
for the series of chromatograms if these analytical parameters remain
constant over the course of the Method 7A analysis.

    Retention time is the elapsed time between  when  the  sample  is
introduced into the  ion  chromatograph and when the peak of interest

-------
                                               Section No. 3.14.5
                                               Date July 1, 1986
                                               Page 6
o
                                               Field Sample: AP-1
                                            Chart Speed: 1 cm/min
                                            Flow Rate: 1.5 ml/min
                                       Detector: 30 yS full sca
                                                 Injection: 50 ui   )
                                               N03  3.3 minutes
                    Inject
Figure 5.2.   Example of chromatogram having adequate documentation.
                                                                O

-------
                                                   Section No. 3.14.5
                                                   Date July 1, 1986
                                                   Page 7

 occurs.   Peaks  on  the  chromatogram may be qualitatively identified by
 retention time.  Retention  times  can be easily computed from chroma-
 tograms  provided that  the injection point  is  indicated  clearly and
 the  chart speed is known.   Identification of the injection  point  is
 necessary because  a chromatogram's trace will not show when injection
 occurred.

     Record the  results  for  the  calibration  standards,  the  field
 samples,  and reagent blank on the appropriate  analytical  data  form
 (Figures  5.3 and  5.4, respectively).   As  discussed  in  Subsection
 2.1.3 and shown in Figure 5.3, the percent deviation  from  the cali-
 bration   curve  of  the  average response  value  for  each  calibration
 standard must be calculated and must be within 7 percent.  A detailed
 discussion of preparation of the calibration curve and calculation of
 the  calibration   factor (S) is found in 3.14.2.  The example data in
 Figure 5.3 shows the use of linear regression to calculate  S  and  a
 non-zero intercept; the example data in Figure 2.3 shows  calculation
 of S with a zero intercept using least  squares.  Equation 2-1 or 2-4
 along with Equation  2-2  (repeated  below) are used -to calculate the
 percent  deviation  using  either  a  zero  intercept  (Eq.  2-1) or a
 non-zero intercept (Eq. 2-4).

                                                         Equation 2-1
    ug NO2  =  S (ug/mm) x Detector (mm)
    Predicted              Response
                              H
                                                         Equation 2-4
    ug N02   = S (ug/mm) /Detector (mm) - I
    Predicted            I Response
                         v   H
')
                                                         Equation 2-2

    Deviation = pg NO2 Predicted - ug NO2 Standard x 1QQ%
      (%)                    ug N02 Standard


    For the analyses of the field samples,  average  the two response
values  .of  each sample (see Figure  5.4).   The  calculated  average
should have units consistent with those of the calibration curve, for
example,  units of peak height, peak area, etc.  The pair of response
values for each sample must each agree within 5 percent of their mean
for  the  analysis to be valid.  For this computation,  the  following
equation is used:

                                                         Equation 5-2

    Deviation (%)  = Instrument Response - Mean Response  x 10Q%
                              Mean Response

-------
Plant
Date
                r
                  I,
 Was an integrator used?  S yes 	no
Location

Analyst
                                                              Section  No.  3-14.5
                                                              Date  July  1,  1986
                                                              Page  8
o
Was the intercept (I) used for calculat
ions? * yes no
Were all points within 7 percent of calculated value? S yes
Sample
Identifier
Std 1
Std 2
Std 3
Std 4
Std 5
Sample
Mass
(Vg NO,)
25
50
100
150
250
Integrator Response
or Peak Height (mm)
H
1
£.3
74.3
2£'5"
30.0
5"M
2
0.4
74.4
26. Z
Vf.O
GO.O
3
#4
t4.z
26.?
37.3
6/jT
Avg
6.3^
74.30
2-6. 53
36-77-
bO.W
Predicted
Sample Mass
23 30
•4&.&I
101-4-1-
/34>o(p
247. fo
no
Deviation
-£.6
--Z..4-
1-1.4-
i-Z.7
- l.v
Predicted Sample Mass using Least Squares to Calculate Calibration Factor  (S)
  with Zero Intercept
S = S1H1
Hl2*
*? - '

* S2H2 + S3H3 + S4H4 + S5H5
H2 + H2 + H2 + R2
)( ) + ( )( ) + ( )( ) * ( )( ) + ( )( C

222??
( r + ( )^ + ( )^ + ( r + ( )2
    S =
            yg N0_/mm
 Predicted Sample Mass  (yg N0?)

  yg N02  = H x S =  {	) x  (	
                                                            Equation 2-1
Predicted Sample Mass using Linear Regression to Calculate Calibration Factor  (S)
  and Non-Zero Intercept (I)
    y = mx + b; m =
    x = - (y - b); i = S =
        m          m
                           _; b =  JL.?5V6  ;

                           -^—  =  4.30/3 ;
    y = H; and b = I (Intercept) =

   Predicted Sample Mass ('yg N0_)

    yg N02 = S(H - I)
    yg N02 at 25 yg standard = 4.30/(  &
                                                         Equation 2-4
        Figure 5'3-   Analytical data form for analysis  of  calibration standards^
                                                                           D

-------
                                                           Section No. 3.14.5
                                                           Date July 1, 1986
                                                           Page 9
                                         5
  Date samples received  3 // 705""    Date samples analyzed

  Plant   /fc>Au   /^tVgK"  rle>*>J- _  Run number(s) AP-^ 2; 5. 4^
  Location
Calibration factor (S)

Reagent blank values:
                              1st,
        Analyst

        Intercept (I), if applicable

        0  2nd,  ^-^)  Avg
                                                                      > f 6



Field
Sample
Number
4f-|
4/-Z
)




Analysis
Number
/sf
j^L




Instrument
Response
(mm)
28.7
23.7



Mean
Instrument
Response
(mm)
2f.sr





Percent
Deviation
(Vg N02)
Z.2.


Mean
Instrument
Response
Blank
Corrected
(H)
Z1.55-

13. /



Dilution
Factor
(F)
,




Mass of
Field
Sample
(yg N02)
//4.4


Deviation of two samples, (#) = 100 x   1 "  21. (must be less than
                              = 100
Mass of field sample
  without intercept
  (VS N0)
Mass of field sample
  with intercept
a S x H x F

= 	 X 	 X 	 =



= S (H - I) F
        Figure 5.4.  Analytical data form for analysis of field samples.

-------
                                                   Section No. 3.14.5
                                                   Date July 1, 1986
                                                   Page 10          x~x

    The reagent blank is analyzed at the  same time as the field sam-5"—'
pies.  The average blank  corrected instrument response (H) is deter-
mined  by  subtracting  the  blank  value from the average instrument
response  for  each sample.  The blank corrected instrument  response
(H),  the  dilution  factor (F), and the calibration factor (S) [with
intercept  (I) if necessary]  are then used  to   calculate the  mass
of N00 per sample as shown in Figure 5.4.
                                                                   o
                                                                  o

-------
                                                              Section 3.14.5
                                                              Date July 1, 1986
                                                              Page 11
                   Table 5.1.  ACTIVITY MATRIX FOR SAMPLE ANALYSIS
 Characteristic
Calibration
  standards
 Acceptance Limits
Data points  for cali-
bration standards must
not deviate  from the
linear calibration
curve by more  than
Frequency and method
    of measurement
Conduct for all analy-
ses of field samples
and calibration stan-
dards
   Action if
 requirements
 are not met
Remake and reana-
lyze standards for
data points  that
do not meet  cri-
teria; interpret
data using another
technique (e.g.
peak area instead
of peak height);
strictly observe
.pipetting tech-
nique; use cali-
bration factor
with y-intercept
for calculations;
calibrate conduc-
tivity detector
Field sample
Results from dupli-
cate analyses must
be within 5 percent
of mean value
Conduct for all
analyses of field
samples
                No results exceeding
                value for calibration
                standard having larg-
                est concentration
                        Applicable to all
                        analyses of field
                        samples; determined
                        by visual inspection
Repeat duplicate
analysis, and
strictly observe
correct pipetting
technique; seek
assistance with
analytical tech-
nique

Dilute blank and
and affected field
sample with equal
volumes of water
and repeat analy-
ses of both
Performance
 audit of
 analytical
 phase
See Section 3.14.8
See Section 3.14.8
See Section 3.14.8
Data
 recording
All pertinent data
recorded on Figs. 5-If
5.2, 5-3, and 5.4
Visually check
Supply missing
data

-------
o
o
o

-------
                                                   Section No. 3.14.6
                                                   Date July 1, 1986
                                                   Page 1
6.0  CALCULATIONS
    Calculation errors due to procedural or mathematical mistakes can
be a large component of total  system error.  Therefore, it is recom-
mended that each set of  calculations  be  repeated  or spot-checked,
preferably by a team  member  other  than  the  one who performed the
original calculations.  If a difference greater than  typical  round-
off error is detected, the calculations  should  be  checked step-by-
step  until the source of error is found and corrected.   A  computer
program  is  advantageous  in  reducing  calculation  errors.   If  a
standardized computer program is used, the original data entry should
be  checked,  and  if  differences are observed, a new  computer  run
should be made.  Table 6.1 at the end of this section summarizes  the
quality assurance activities for calculations.

    Calculations  should  be  carried  out at least one extra decimal
figure  beyond that of the acquired data, and should be rounded after-
final calculation to two significant  digits  for each run or sample.
All  rounding  of  numbers should be performed in accordance with the
ASTM 380-76 procedures.  All calculations are then recorded on a form
such as the one in Figure 6.1A.

6.1  Nomenclature

     The following nomenclature is used in the calculations:

    P- = final absolute pressure of flask, mm (in.) Hg,

    P.  = initial absolute pressure of flask, mm (in.) Hg,

  Pstd = s-tandard absolute pressure,  760 mm (29.92 in.) Hg,

    Tf = final absolute temperature of flask,  °K (°R),

    T.  = initial absolute temperature of flask,  °K (°R),

  Tstd = standard absolute temperature,  293°K (528°R),

   V   = sample volume at standard conditions, dry basis,  ml,
    SO

    Vf =! volume of flask and valve,  ml,

    V_ = volume of absorbing solution, 25 ml,
     cl

     H = sample peak height or area (blank should be subtracted
         out),  mm,

     F = dilution factor (required only if additional sample
         dilution was needed to reduce the concentration into
         the range of calibration),

     C = sample concentration of NO  as N00, mg/dscm,
      .                             X      £t

-------
                                                   Section No. 3.14.6
                                                   Date July 1, 1986
                                                   Page 2
    S = calibration factor, u g/mm, and

    I = intercept term from calibration equation, mm.

6.2  Calculations

    The following four  Subsections outline the procedures for calcu-
lating the concentration of nitrogen oxides  in  samples.  Subsection
6.2.1 presents the equation for calculating  the  sample  volume on a
dry basis at standard conditions.

    Subsection 6.2.2 presents the equation for calculating the sample
concentration  of  nitrogen oxides as it appears in Method 7A.   This
equation utilizes  tho  calibration  factor,  S, determined during the
calibration of the ion chromatograph (see Subsection 2.1.3 of Section
3.14.2).  Subsection 6.2.3 offers an alternative approach  acceptable
to  the  Administrator  for  calculating the sample concentration  of
nitrogen  oxides' utilizing the calibration factor, S, and the inter-
cept  term,  I, from the  calibration  equation.   This  equation  is
determined  following  the  procedures  outlined  in  Method  7D  for
calibration of the ion chromatograph (see Subsection 2.1.3 of Section
3.14.2).
o
    Subsection 6.2.4 presents a simple equation for converting sample
concentration  to  parts  per million.  Examples  of  nitrogen  oxide
calculation forms are presented at the end of each section and should
be used with the appropriate calculation methodology.
6.2.1  Sample Volume - Calculate the sample volume on a dry  basis at
standard conditions  [760  mm  (29.92  in.)  Hg and 293 K (528 R)] by
using the following equation.

               T   rv  - v ^   /P    P v                 Equation 6-1
         Ve^ = *stdtvf   va;   I If. _ _1 »
                  P            \ T    T
                  *std         W   Ai


             = Ki(Vf - 25 ml)  /Pf _ ^1


where

                       °K
         K. = 0.3858	—- for metric units, or
                     mm Hg

         K. - 17.64   °R  for English units.
                   in. Hg

6.2.2  Sample Concentration Using the Calibration Factor, S  - Calcu-
late  the sample concentration on a dry basis at standardconditions
using the calibration factor, S,  as shown in Equation  6-2  when  the
calibration factor S was calculated with  no  intercept.  See Figures
O
                                                                    O

-------
                                                   Section No. 3.14.6
                                                   Date July 1, 1986
                                                   Page 3

6.1A and 6.IB for examples  of  calculation  forms  for  English  and
metric units, respectively.

                                                         Equation 6-2
         c _ HSF x 104
where
               Vsc
         4
       10  =1:10 dilution times conversion factors of

                 mg          106 ml
6.2.3   Sample  Concentration  Using  the  Calibration  Equation  and
Factor, S -  Calculate  the  sample  concentration  on a dry basis at
standard conditions  using  the  calibration factor and the intercept
term for the calibration  equation  as  shown  in  Equation 6-3.  See
Figures 6.1A and 6. IB  for  examples of calculation forms for English
and metric units, respectively.

    _   K (H-I) SF x 104                                 Equation 6-3

         2~^

where

    K2 = 1 for metric units, or

    K9 = 6.243 x 10~8  dscm/mg for English units.
                       dscf/lb
     4
   10  =1:10 dilution times conversion factors of

                 mg        10  ml
                 3            3
               10  yg        m   .

6.2.4  Sample Concentration  in  Parts-Per-Million  - If desired, the
concentration  of  NO2  may  be  calculated  as  ppm N02 at  standard
conditions using Equation 6-4 as shown below.

                                                        Equation 6-4
    ppm
where
    K3 = 0.5228 — ppm N°2 - for metric units, or
                 mg N02/dscm
     « = 8.375 x 106 - PPm NO2 - fQr English units
                     Ibs NO2/dscf
                                             llM

-------
                                            Section No.  3.14.6
                                            Date July 1,  1986
                                            Page 4



                        Sample Volume


 Vf = 2-Oi 3 ml, Pf = 2-7 .  (ff 4 in.  Hg,  Tf = <>5_3_ °R

 P. =   0 .  5" 7 in. Hg, T. =  5 32..  °R
  i   — —   — ->-          i   — — —

                       /P    P \    ,-»/?*          Equation 6-1
V   = 17.64 (V. - 25)  /  f    i 1 = / 7 0 0 ml
 sc           ±
                       )   /ff _
                          \Tf   TJL
                        Sample Concentration

(No Intercept Used)

    H =	.	mm,  S = _	yg/mm,

    F =	,  V   =	ml                        ,

                                                       Equation 6-2
                  — R HCTT v TO                  — R
    C = 6.243 x 10 ° "ar x -1"  =     .      x 10   Ibs N00/dscf
                        V                               2
                         sc


(With Intercept Used)

    H = 2-3 . j_ 0_ mm,  I = _ Z-. ^^Tmm,  S = T-3^ ]_ ug/mm,

    F = _ 1-0,  Vsc = _/7 ^ 0 ml

                                                    - . . Equation 6-3
                                 4
    C = 6.243 x 10"8 (H"I)SF x 10  = _ 3 .  0 f x 10~5 Ibs N0,/dscf

                           Vsc



                    Sample Concentration in ppm

                        ,.                              Equation 6-4
    ppm NO,, = 8.375  x 10  C =   2- 5" 5~ppm N00
          ^/                   —. — —         ^/
    Figure 6.1A.   Nitrogen oxide calculation form (English units)
                                                              •o

-------
                                                Section No.  3.14.6
                                                Date  July 1,  1986
                                                Page  5
   V
    sc
                           Sample Volume


         J-2 L 2 ml, Pf = 7 0 t. Q mm Hg, Tf  =  2- j_

         _ ]_ *$_. Q_ mm Hg, T± = _2-f 5_. 5"°K

                           /p    p v          _
         0.3858 (V. - 25)  /  f    i 1 =  / 7 £ S . ml
                               "         ---
                                                     .  L °K
                                                        Equation 6-1
                        Sample Concentration


(No Intercept Used)

      H =  _ _. _ _ mm,   S = _ _ _ _ v g/mm


      F = _ _  .  vsc =	ml
                  O w
      c =
          HSF x 10'
              sc
                               x 10  mg NO0/dscm
(With Intercept Used)



    F -   A 0. v_ = / 7
                                                       Equation  6-2
                                      ' s =  4.$ 0 ]_  yg/mm,
                             ml
                                                       Equation  6-3
      = (H-I)SF x

           Vsc
                      = ^ • Z .!•? _ x 10  m9 N02/dscm
                    Sample Concentration in ppm
                                                       Equation  6-4
    ppm N00 = 0.5228 C =   2-    ppm N0
                         — — — —
    Figure 6.IB.   Nitrogen oxide calculation form (metric units).

-------
                                         Section No.  3.14.6
                                         Date July 1, 1986
                                         Page 6
Table 6.1.  ACTIVITY MATRIX FOR CALCULATIONS
o
Characteristics
Sample volume
calculation
Sample mass
calculation
Sample concen-
tration
Calculation
check
Document and
report re-
sults
Acceptance limits
All data available;
calculations correct
within round-off error
As above
As above
Original and checked
calculations agree
within round-off error
All data available;
calculations correct
within round-off error
Frequency and method
of measurement
For each sample, exam-
ine the data form
As above
As above
For each sample, per-
form independent cal-
culation using data on
Figs. 4.1, 4.2, and
4.3
For each sample, exam-
ine the data form
Action if
requirements
are not met
Complete the
data, or void
the sample
As above
As above
Check and
correct all
data
Complete the (
data, or void ^^
the sample
                                                            O

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                                                   Section No. 3.14.7
                                                   Date July 1, 1986
                                                   Page 1
     MAINTENANCE
    The normal use  of emission-testing equipment subjects it to cor-
rosive gases, extremes in temperature, vibration, and shock.  Keeping
the equipment in good operating order over an extended period of time
requires knowledge of the equipment and a routine maintenance program
which should be performed quarterly or upon improper  functioning  of
the apparatus.  As for Method 7, it is suggested that the vacuum pump
be disassembled and cleaned yearly.  A summary of the components with
maintenance procedures  is  presented in Table 7.1 at the end of this
section.   These 'procedures are not required, but are recommended  to
increase the reliability of the equipment.

7.1  Pumps

    Several types of pumps are used in  the  present commercial samp-
ling  trains.   The  two  most  common are the fiber vane  pump  with
in-line oiler and the diaphragm pump.  The fiber vane pump requires a
periodic  check  of  the  oiler jar.  The oil should be  translucent.
During the yearly disassembly or if the fiber vane pump starts to run
erratically, the head should  be removed and the fiber vanes changed.
The  diaphragm  pump  will  show  a  leak  when  the  diaphragm needs
changing.   If the diaphragm pump runs erratically, it is usually due
to  a bad diaphragm (causing  leakage)  or  to  malfunctions  in  the
valves.   The  valves  should  be  cleaned   annually   by   complete
.disassembly of the pump.

7.2  Shipping Containers

    Since the majority of the sampling  train is glassware, the ship-
ping  containers  are  very important for protection and safety.  All
shipping   containers   should  be  inspected  quarterly  for   their
condition,  and  repaired  or  modified  to  assure the safety of the
equipment.

7.3  Ion Chromatograph

    Maintenance activities and schedules  for  ion chromatographs are
make and model  specific.   It  is  therefore  recommended  that  the
analyst  consult  the  operator's manual for instructions relative to
maintenance practices and procedures.

    Guard columns, while not required,  are  recommended £gr use with
the ion chromatograph in order to extend column lifetime.

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                                   Section No. 3-14.7
                                   Date July 1, 1986
                                   Page 2
o
Table 7.1.  ACTIVITY MATRIX FOR MAINTENANCE

Apparatus
Fiber vane pump
Diaphragm pump
Shipping con-
tainer
Ion chrom-
atograph
Acceptance criteria
Oil translucent; pump
leakless and capable
of pulling a vacuum of
less than 75 mm (3
in. ) Hg absolute
pressure
Leak free, valves
functioning properly,
and capable of pulling
a vacuum of < 75 mm
(3 in. ) Hg absolute
pressure
Protect equipment from
damage
See owner's manual
Frequency and method
of measurement
Check oiler jar
periodically; remove
head and change fiber
vanes
Clean valves during
disassembly; replace
diaphragm as needed
Inspect quarterly;
repair as needed
See owner's manual
Action if
requirements
are not met
Replace as
needed
Replace when
leaking or mal-
functioning
Replace f
See owner's
manual
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                                                   Section No. 3.14.8
                                                   Date July 1, 1986
                                                   Page 1
 8.0  AUDITING PROCEDURE
    An  audit is an independent assessment of data quality.  Indepen-
 dence is achieved if the individual(s) performing the audit and their
 standards and equipment are different from the regular field team and
 their standards and equipment.  Routine quality assurance checks by a
 field team are necessary  to generate good quality data, but they are
 not part of the auditing  procedure.   Table  8.1  at the end of this
 section summarizes the quality assurance functions for auditing.
                                               19 20 21
    Based on the results of collaborative tests  '  '    of Method 7,
 two specific performance audits are recommended:

    1.  Audit of the analytical phase of Method 7A.
    2.  Audit of data processing.

 It is suggested that a systems audit be conducted as specified by the
 quality assurance  coordinator,  in  addition  to  these  performance
 audits.   The  two  performance  audits  and  the  systems  audit are
 described in detail in Subsections 8.1 and 8.2, respectively.

 8.1  Performance Audits

    Performance  audits are made to evaluate quantitatively the qual-
 ity  of data produced by the total measurement system (sample collecj-
 tion,  sample analysis, and data processing).  It is  recommended that
 these audits be performed  by  the  responsible  control  agency once
 during every enforcement source test.   A source test for enforcement
 comprises a series of runs  at  one,.source.  The performance audit pf
 the analytical  phase  is  subdivided  into  two steps: (1) a pretest
 audit which is optional,   and  (2) an audit during the field sampling
 and/or analysis phase which  is required.  No audit is recommended at
 this time for the sample collection phase.                       .-i:"v"

 8.1.1  Pretest  Audit  of  Analytical  Phase (Optional) - The pretest
 audit described in this section can  be  used  to  determine the pro-
 ficiency of. the analyst,   the quality of the  standard  solutions  in
the Method  7A  analysis,  and the ability to perform the computations
correctly.   It  should  be  performed at the discretion of the agency
 auditor,  the laboratory  supervisor,  source test company, or quality
 assurance officer.   The analytical phase  of Method 7A can be audited
with the use of aqueous potassium or sodium nitrate samples.  Aqueous
 sodium nitrate samples  may  be  prepared  using  the  same procedure
 described in Section 3.14.2 for calibration standard preparation.

    The  pretest  audit  provides  the  opportunity  for  the testing
 laboratory to check the accuracy of  its  analytical procedure.  This
 audit  is especially recommended for a laboratory with little  or  no
 experience  with  the  Method 7A analysis procedure described in this
Handbook.

    As  an  alternative to preparing their own audit  samples  for  a
pretest audit,  a testing laboratory may,  30 days prior to the time of

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                                                   Section No.  3.14.8
                                                   Date July 1,  1986
                                                   Page 2

the planned pretest  audit,  make  a  request  to EPA's Environmental(   )
Monitoring Systems  Laboratory,  Quality  Assurance  Division,  Source^—-/
Branch, Mail Drop 77A, Research  Triangle Park, North Carolina  27711
for  known  quality  control  samples.   These  samples  are  aqueous
potassium nitrate samples (and not sodium nitrate samples).

    The relative error for  each  of  two samples should be within 10
percent of true  value.   The relative error (RE) is an indication of
the bias that may be associated with the  analytical  phase of Method
7A.  Calculate RE using Equation 8-1.
                RE = Cd " Ca x 100

                       Ca
                                                         Equation 8-1
where
    C, = Determined audit sample concentration, mg/dscm, and

    C  = Actual audit sample concentration, mg/dscm.
     a
8.1.2  Audit of Analytical Phase of the Field Test  (Required)  -  As
stated in Sections  3.3.9  and 4.4 of 40 CFR 60, Appendix A, Method 7
(49  FR  26522, 06/27/84), when the method is  used  for  enforcement
testing, the analyst must analyze two audit  samples  along  with thp"~N
field  samples.   The  testing laboratory should notify  the  responl  j
sible agency requiring  the performance test of the intent to test ar""*'^
least 30 days prior to the  enforcement source test.  The responsible
agency will provide two audit samples to be  analyzed  along with the
field  samples from the enforcement source test.  The purpose of this
audit is to assess the data quality at the time of the analysis.   If
EPA  is  the agency  requiring  the  performance  test,  the  testing
laboratory should notify the Quality Assurance Management  Office  in
the  respective  EPA  Regional  Office.   The addresses  of  the  EPA
Regional Quality Assurance Coordinators  are  shown  in  Table 5.1 of
Section 3.0.5 of this Handbook.

     The two audit samples and the compliance samples must be concur-
rently analyzed in the same manner  to  evaluate the technique of the
analyst, the standards  preparation,  and computation skills.  (Note:
It is recommended that known  quality  control  samples  be  analyzed
prior to the compliance  and  audit  sample  analysis to indicate any
problems.  One source of these samples is the Source Branch listed in
Subsection  8.I.T.)   The  same  analyst,  analytical  reagents,  and
analytical system  shall  be used both for compliance samples and the
EPA audit samples; if this  condition  is met, auditing of subsequent
compliance  analyses  for  the same enforcement agency within 30 days
may not be required.  An audit sample set may not be used to validate
different  sets  of  compliance samples  under  the  jurisdiction  of
different  enforcement agencies,  unless prior;arrangements  are  made
with both enforcement agencies.
o

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                                                   Section No. 3.14.8
                                                   Date July 1, 1986
                                                   Page 3

     Calculate the concentrations  in  mg/dscm  using  the  specified
sample  volume in the  audit  instructions.   (Note:   Indication  of
acceptable results may be obtained immediately by reporting the audit
results in mg/dscm and compliance  results  in total mg N02/sample by
telephone  to  the  responsible  enforcement  agency.)   Include  the
results of both audit samples, their  identification numbers, and the
analyst's  name - with  the  results  of  the compliance determination
samples  in  appropriate  reports to the EPA Regional Office  or  the
appropriate  enforcement  agency.   Include  this   information  with
subsequent compliance analyses for the same enforcement agency during
the 30-day period.

     The concentration of each audit sample measured by  the  analyst
shall  agree  within  10 percent of the actual concentration.  If the
10-percent specification is not met, reanalyze the compliance samples
and audit samples, and  include  initial and reanalysis values in the
test report.

     Failure to meet the 10-percent specification may require retests
until the audit problems are resolved.  However, if the audit results
do not affect the compliance or noncompliance  status of the affected
facility,  the Administrator  may  waive  the  reanalysis requirement,
further audits, or retests and accept  the  results of the compliance
test.   While  steps  are being taken to resolve audit analysis prob-
lems, the Administrator  may also choose to use the data to determine
the compliance or noncompliance  status  of  the  affected  facility.
Other  applications  of  Method  7A (i.e., Performance  Specification
Tests) should follow agency recommended or required procedures.

8.1.3   Audit.QfgDa^a Processing - Calculation  errors  are prevalent
in  Method 7.-LJ'-u> ~xData processing errors can  be  determined  by
auditing  the recorded data on the field and laboratory  forms.   The
original and audit (check) calculations should agree within round-off
error; if not,  all of the remaining data should be checked.  The data
processing  may  also be audited by providing the testing  laboratory
with specific  data  sets (exactly as would appear in the field), and
by requesting that the data calculation  be  completed  and  that the
results be returned to the agency/organization.  This audit is useful
in  checking  both computer  programs  and  manual  methods  of  data
processing.

8.2  Systems Audit

     A systems audit is an on-site qualitative  inspection and review
of the total measurement system (sample collection,  sample analysis,
etc.).  Initially, a systems audit  is  recommended for each enforce-
ment source  test,  defined  here  as  a  series of three runs at one
source.  After the test team gains experience  with  the  method, the
frequency  of audit may be reduced—for example, to  once  for  every
four tests.

     The  auditor  should  have extensive  background  experience  in
source  sampling,  specifically  with  the  measurement  system  being
audited.  The functions of the auditor are summarized below:
                                                     r;

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          -  .                                       Section No.  3.14.8
                                                   Date July 1,  1986
                                                   Page 4

     1.    Inform  the testing team of the results of pretest audits,
specifying any area(s) that need special attention or improvement.

     2.   Observe procedures and techniques  of the field team during
sample collection.

     3.   Check/verify records  of  apparatus  calibration checks and
quality control used in the laboratory  analysis  of  control samples
from previous source tests, where applicable.

     4.    Record  the results of the audit,  and  forward  them  with
comments to the team management so that appropriate corrective action
may be initiated.

     While  on  site, the auditor observes  the  source  test  team's
overall performance, including the following specific operations:

     1.   Setting up and leak testing the sampling train.

     2.   Preparing the absorbing solution (if performed on-site) and
adding it to the collection flasks.

     3.   Collecting the sample.

     4.    Sample   absorption   procedures,    sample  recovery,  and
preparation of samples for shipment.

Figure 8.1 is a suggested checklist for the auditor.
                   o
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                                                              Section No.  3.14.8
                                                              Date July 1,  1986
                                                              Page 5
Yes
No
Comment
                               Presampling preparation

                      1.    Plant operation parameters variation

                      2.    Calibration of the flask and valve volume	three
                            determinations

                      3.    Absorbing reagent preparation
                5.
                                On-site measurements

                            Leak testing of sampling train

                            Preparation and introduction of absorbing solution
                            into sampling flask
                                    Postsampling
                             (Analysis and Calculation)

                      6.     Control sample analysis

                      7.     Sample aliquotting techniques

                      8.     Ion chromatographic technique

                             a. Preparation of standard nitrate samples
                                (pipetting)
                             b. Calibration factor (+^ 7 percent for all
                                standards)
                             c. Duplicate sample values within 5 percent
                                of their mean
                             d. Adequate peak separation

                       9.  Audit results (+ 10%)

                            a.  Use of computer program
                            b.  Independent check of calculations
                                      Comments
              Figure 8.1.   Method 7A checklist to be used by auditors,

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                                                              Section No. 3.14.8
                                                              Date July 1, 1986
                                                              Page 6
               Table 8.1.  ACTIVITY MATRIX FOR AUDITING PROCEDURE
                                                                  o
Audit
 Acceptance Limits
Frequency and method
    of measurement
  Action if
requirements
are not met
Performance
  audit of
  analytical
  phase
Measured RE of the
audit samples shall
be within 102 for
both audit results
Frequency; Once during
every enforcement source
test*
Method; Measure QA sam-
ples and report values
to responsible agency
Review operating
technique and/or
calibration check
Data
  processing
  errors
Original and checked
calculations agree
within round-off
error
Frequency; Once during
every enforcement
source test
Method; Independent
calculations starting
with recorded data on
Figures 4.1 and 5-1
Check and correct
all data for the
audit period rep-
resented by the
sampled data
Systems
  audit-
  observance
  of tech-
  nique
Operational tech-
nique as described
in this section of
the Handbook
Frequency; Once during
every enforcement source
test until experience
gained, then every
fourth test
Method; Observation of
techniques assisted by
audit checklist,
Fig. 8.1
Explain to team
their deviation
from recommended
techniques, and
note on Fig. 8.1
D
*As defined here, a source test for enforcement of the NSPS comprises a series
 of runs at one source.  Source tests for purposes other than enforcement (e.g.,
 a research project) may be audited at a lower frequency.
                                                                                 O

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                                                   Section No. 3.14.9
                                                   Date July 1,  1986
                                                   Page 1

9.0  RECOMMENDED STANDARDS FOR ESTABLISHING TRACEABILITY

    To achieve data of desired quality,  two essential considerations
are necessary: (1) the measurement  process  must  be  in  a state of
statistical  control  at the time of the  measurement,  and  (2)  the
systematic errors, when combined with the random variation (errors or
measurement),  must result in an acceptable uncertainty.  As evidence
in support of good quality data,  it  is necessary to perform quality
control  checks and independent audits of the measurement process; to
document these data;  and to use materials, instruments, and measure-
ment procedures that can be traced  to  an  appropriate  standard  of
reference.

    Data must be routinely obtained by  repeat  measurements of stan-
dard reference samples (primary, secondary, and/or working standards)
and the establishment of a condition of process control.  The working
calibration  standards  should  be  traceable  to standards of higher
accuracy.

    Class-S weights (made to NBS specifications)  are recommended for
the analytical balance calibration.  See Section 3.6.2 for details on
balance calibration checks.

    Class-A volumetric flasks and pipets (made to NBS specifications)
should be used in the preparation and transfer of solutions.

    Audit samples (as discussed in Section  3.14.8)  must  be used to
validate test results for compliance determination  purposes  and are
recommended  as  an independent check on the measurement process when
the method is performed for other purposes.
                                                (I

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   10.0    REFERENCE  METHOD*
                                                                              Section No.  3.14.10
                                                                              Date  July  1,   1986
                                                                              Page  1
 METHOD  7A—DETERMINATION  or  NITROGEN
   OXIDE   EMISSIONS  FROM   STATIONARY
   SOURCES—ION CHROMATOORAPHIC METHOD


   1. Applicability and Principle.
   1.1  Applicability. This method applies to
 the measurement of nitrogen oxides emitted
 from stationary sources:  it may be used as
 an alternative to Method 7 (as defined In 40
 CFR Pan 60.8(b)) to determine compliance
 If the stack concentration Is within the ana-
 lytical range. The analytical ranee of  the
 method is from 125 to 1.230 mg NO./m1 as
 NOi (65 to 655 ppm). and higher concentra-
 tions  may  be  analyzed  by   diluting  the
 sample. The lower  detection limit Is  ap-
 proximately  19 mg/m' (10 ppm). but may
 vary among instruments.
  1.2 Principle. A grab sample is collected
 in an evacuated flask containing a diluted
'sulfuric acid-hydrogen peroxide absorbing
 solution.  The nitrogen oxides, except  ni-
 trous oxide,  are  oxidized to nitrate and
 measured  by ion chromatography.
  2. Apparatus.
  2.1 Sampling. Same as In Method 7, Sec-
 tion 2.1.
  2.2 Sampling   Recovery.  Same  as   In
 Method 7. Section 2.2. except the stirring
 rod and pH paper are not needed.
  2.3 Analysis. For the analysis, the follow-
 ing equipment is needed. Alternative Instru-
 mentation and procedures will be  allowed
 provided the calibration precision In Section
 5.2 and acceptable audit  accuracy can be
 met.
  2.3.1 Volumetric Pipets. Class A: 1-. 2-, 4-.
 5-ml (two  for the set of standards and one
 per  sample).  6-,  10-,  and graduated 5-ml
 sizes.
  2.3.2 Volumetric Flasks. 50-ml (two per
 sample and one per standard). 200-ml. and
 1-llter sizes.
  2.3.3  Analytical Balance. To measure to
 within 0.1  mg.
  2.3.4  Ion Chromatograph. The ion chro-
 matograph should have at least the follow-
 ing components:
  2.3.4.1  Columns. An artion separation or
 other column capable of resolving the  ni-
 trate ion  from sulfate and other species
 present and  a, standard  anion suppressor
 column (optional). Suppressor  columns  are
 produced as proprietary items: however, one
 can be produced in the laboratory using the
 resin available from BioRad Company. 32nd
 and Griffin Streets. Richmond. California.
  2.3.4.2 Purap. Capable  of maintaining a
 steady flow as required by the system.
  2.3.4.3 Flow Gauges. Capable of measur-
 ing the specified system flow rate.
  2.3.4.4 Conductivity Detector.
  2.3.4.5 Recorder.  Compatible with  the
 output voltage range of the detector.
   3. Reagents.
   Unless otherwise indicated. It is Intended
 that all reagents conform to the specifica-
 tions established by the commit^* on Ana-
 lytical Reagents of the American Chemical
 Society, where such specifications are avail-
 able: otherwise, use the best available grade.
   3.1 Sampling. An absorbing solution con-
 sisting of suliuric acid (HiSO.) and hydro-
 gen peroxide (ffiOi)  is required for sam-
 pling. To  prepare  the absorbing solution, i
 cautiously add 2.8 ml concentrated H.SO. to
 a 100-ml flask  containing water (same as
 Section  3.2),  and  dilute  to  volume with
mixing. Add 10  ml  of  this solution, along
with 6 ml of 3 percent  HiOi that has been
freshly prepared from  30 percent solution.
to a 1-liter flask.  Dilute to volume with
water and mix well. This absorbing solution
should b« used within 1  week of Its prepara-
tion. Do  not expose to extreme heat or
direct sunlight.
  3.2  Sample Recovery. Deionized distilled
water that conforms to American Society
for Testing and Materials specification D
1193-74. Type 3. is required for sample  re-
covery. At  the  option  of the analyst, the
KMnO. test for oxidizable organic matter
may be omitted when  high concentrations
of organic  matter are  not expected to b«
present.
  3.3  Analysis. For the  analysis, the follow-
ing reagents are required:
  3.3.1  Water. Same as  In Section 3.2.
  3.3.2  Stock Standard  Solution. 1 mg NO,/
ml. Dry an adequate amount of sodium ni-
trate (NaNO.) at 105 to 110'C for a mini-
mum of 2 hours just before preparing the
standard  solution.   Then dissolve exactly
1.847 g of dried NaNO,  In water, and dilute
to 1 liter in a  volumetric  flask.  Mix well.
This solution  Is stable for 1  month and
st.ould not be used beyond this time.
  3.3.3  Working Standard Solution. 25 n«/
ml. Dilute 5 ml of the standard solution to
200 ml with water In a volumetric  flask, and
mix well.  •

  3.3.4  Eluent Solution. Weight 1.018 g of
sodium carbonate (Na»CO>) and 1.008 g of
sodium bicarbonate  (NaHCOj). and dissolve
In 4 liters of water. This solution is 0.0024 M
NatCOi/0.003 M NaHCO, Other eluents ap-
propriate to the column type and capable of
resolving nitrate ion from sulfate and other
species present may be used.
  3.35 Quality  Assurance  Audit Samples.
Same as required in Method 7.
  4. Procedure.
  4.1  Sampling. Same as In Method 7. Sec-
tion 4.1.
  4.2  Sample.   Recovery.   Same  as  In
Method 7,  Section  4.2, except delete the
steps on  adjusting and  checking the  pE of
the sample. Do not  store the samples more
than 4 days between collection and analysis.
     Federal  Register,  Volume  48,  No.  237,   December  8,   1983.
                                                                                           ,77/3

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  4.3  Sample.  Preparation. Note the level
of the liquid In the container and confirm
whether any sample was lost during ship-
ment; note this on the analytical data sheet.
If a noticeable amount of leakage  has oc-
curred, either void the sample or use meth-
ods, subject to the approval of the Adminis-
trator, to correct the final results. Immedi-
ately before analysis, transfer the contents
of the shipping container to a 50-ml volu-
metric flask, and rinse the container twice
with 5-ml portions of water. Add the rinse
water to the flask, and dilute to the mark
with water. Mix thoroughly.
  Pipe: a 5-ml aliquot of the sample Into a
50-ml volumetric flask, and dilute to the
mark with water. Mix thoroughly. For each
set of determinations,  prepare a reagent
blank by diluting 5 ml of absorbing solution
to 50 ml with water. (Alternatively,  eluent
solution may be used in all sample, stand-
ard, and blank dilutions.)
  4.4  Analysis. Prepare a standard calibra-
tion curve according to Section 5.2. Analyze
the set of standards followed by the set of
samples using the same injection volume for
both standards  and samples. Repeat  this
analysis sequence followed by a final analy-
sis of the standard set. Average the  results.

The two  sample values must agree within 5
percent of their mean for the anlaysls to be
valid. Perform this duplicate analysis  se-
quence on the tame day. Dilute any sample
and the blank with equal  volumes of water
if  the  concentration exceeds that  of the
highest standard.
  Document each sample chromatogram by
listing the following analytical parameters:
injection  point, injection  volume,  nitrate
and tulfate retention times, flow rate, detec-
tor sensitivity setting, and recorder chart
speed.
  4.5  Audit Analysis. Same as required in
Method 7.
  5. Calibration.
  5.1  Flask  Volume. Same as In Method 7,
Section 5.1.
  5.2  Standard Calibration Curve. Prepare
a series of five standards by adding 1.0. 2.0,
4.0. 6.0. and 10.0 ml of working standard so-
lution (25 MC/rol) to a series of five 50-ml
volumetric flasks. (The standard masses will
equal 25. 50. 100. 150, and 250  us.) Dilute
each  flask to volume with water,  and mix
well. Analyze with the samples as described
In Section 4.4 and subtract the blank from
each value.  Prepare or calculate a linear re-
gression  plot to the standard masses in >ig
(x-axis> versus their peak  height responses
in millimeters  (y-axls). (Take peak  height
measurements  with symmetrical peaks;  In
all other cases, calculate peak areas.) From
this curve, or equation, determine the slope,
and calculate Its reciprocal to denote as the
calibration factor, S. If any  point deviates
from the line by more than 7 percent of the
concentration at that point, remake and re-
analyze that standard. This deviation can be
determined  by multiplying S times the peak
height response for each  standard. The re-
sultant concentrations must not differ by
more than  7  percent  from  each  known
standard mass (I.e.. 25. 50. 100, ISO, and 250
MB)-
                                                                                Section No.  3.14.10
                                                                                Date  July  1,  1986
                                                                                Page  2
    5.3  Conductivity Detector. Calibrate ac
  cording  to  manufacturer's  specifications
  prior to Initial use.
    5.4  Barometer. Calibrate against  a mer-
  cury barometer.
    5.5  Temperature  Gauge.  Calibrate dial
  thermometers   against   mercury-in-glass
  thermometers.
    5.6  Vacuum Gauge. Calibrate mechanical
  gauges, if used, against  a mercury manome-
  ter such as that specified in Section 2.1.6 of
  Method 7.

  5.7  Analytical Balance. Calibrate against
standard weights.
  6. Calculation*.
  Carry out the  calculations, retaining at
least  one extra decimal figure beyond  that
of  the  acquired  data. Round off figures
after  final calculations.
  6.1  Sample Volume. Calculate the sample
volume  V« (in ml) on a dry basis, corrected
to standard  conditions, using Equation 7-2
of Method 7.
  6.2  Sample Concentration of NO, as NO,.
Calculate  the  sample concentration C (in
mg/dscm) as follows:
o
           HSP X 10«
                                 . 7A-1
Where:
H "Sample peak height, mm
S = Calibration factor, ^.g/rnm
F -Dilution factor (required only If sample
   dilution was  needed to  reduce the con-
   centration into the range of calibration)
10* - 1:10 dilution  times conversion factor
   of
O
              mg
                      10'ml
  If desired, the concentration of NOi may
be calculated as ppm NOt at standard condi-
tions as follows:
      ppm NOi - 0.5228 C    Eq. 7A-2


Where:
0.5228 - ml/mg NO,.
                                         O

-------
                                                                       Section  No.  3.14.10
                                                                       Date  July  1,  1986
                                                                       Page  3
  7. Biblioyravtiy.
  1. Mulik, J. D. and E. SawicW. Ion Chro-
matographic Analysis of Environmental Pol-
lutants. Ann Arbor. Ann Arbor Science Pub-
lishers. Inc. Vol. 2. 1979.
  2. SawicW. E.. J. D. Mulik. and E. Wittgen-
stein. Ion Chromatographic Analysis of En-
vironmental  Pollutants.  Ann Arbor. Ann
Arbor Science Publishers. Inc. Vol. 1.1978.
  3. Sterner,  D. D. Separation of Chloride
and Bromide from Complex  Matrices Prior
to Ion Chromatographic Determination. An-
alytical Chemistry 52(12:1874-1877). Octo-
ber 1980.
  4. Small,  H.. T. S. Stevens, and W. C.
Batunan. Novel Ion Exchange Chromatogra-
phic Method Using Conductimetric Deter-
mination. Analytical Chemistry. 47(11:1801).
1975.
  5. Yu. BUng K. and Peter R. Westlin. Eval-
uation  of Reference Method 7 Flask Reac-
tion Time. Source Evaluation Society News-
letter. 4(4). November 1979.10 p.

-------
o
o
o

-------
                                                  Section No. 3.14.11
                                                  Date July 1, 1986
                                                  Page 1
11.0  REFERENCES

      1.
     10,
     11.
     12.
     13,
Federal  Register,  Volume  48, No. 237, December 8,   1983.
Method 7A - Determination  of Nitrogen Oxide Emissions From
Stationary Sources.

Small, H. T., S. Stevens,  and  W.  C.  Bauman.  rNovel Ion
Exchange  Chrbmatographic   Method   Using   Conductimetric
Determination.  Analytical Chemistry,  47(11):801, 1975.

Johnson,   E.   L.   and   R.   Stevenson.    Basic  Liquid
Chromatography.  Varian Associates, Inc., 1978.

Yost,  R.  W.,  L.  S.  Ettre,  and R. D. Conlon, Practical
Liquid  Chromatography,  An   Introduction.   Perkin-Elmer,
1980.
          Smith,   F.   C.,
          Chromatography.
          1983.
                 Jr., and R. C. Chang.  The Practice of Ion
                  John  Wiley  and  Sons,  Inc.,  New York,
Stevens, T. S. and M. A. Langhorst. Agglomerated Pellicular
Anion-Exchange  Columns for Ion Chromatography.  Analytical
Chemistry, 54 (6):950, 1982.

Stevens, T. S., G. L. Jewett, and  R.  A. Bredeweg.  Packed
hollow    fiber   suppressors   for   ion   Chromatography.
Analytical Chemistry, 54 (7):1206, 1982.

Mulik,   J.   D.,  and  E.  Sawicki.   Ion  Chromatography.
Environmental Science and Technology, 13 (7):804, 1979.

Stevens, T. S., J. C. Davis, and H. Small. Hollow Fiber Ion
Exchange  Suppressor  for  Ion  Chromatography.  Analytical
Chemistry, 53 (9):1488, 1981.

Stevens,  T.  S.   Packed  fibers  and  new  columns speed,
simplify   ion  Chromatography.   Industrial  Research  and
Development, September 1983.

Gjerde,  D.  T.,  J.  S.  Fritz,  and-G.- Schmuckler.  Anion
Chromatography  with Low-Conductivity Eluents.  Journal  of
Chromatography, 186 (509), 1979.

Jupille, T., D. Burge,  and  D. Togami.  Ion Chromatography
uses only one column  to  get  all  the ions.  Research and
Development 26 (3):135, 1984.

Jenke,   D.    Anion  Peak  Migration  Ion  Chromatography.
Analytical Chemistry, 53 (9):1535, 1981.

-------
                                             Section No. 3.14.11
                                             Date July 1, 1986
                                             Page 2
14.  Skoog, D. A., and D. W. West.  Fundamentals  of  Analytical
     Chemistry,  Second  Edition.   Holt,  Rinehart and Winston,
     Inc., New York, 1969.

15.  Yu, King  D. and Peter R. Westlin.  Evaluation of Reference
     Method 7 Flask Reaction Time.   Source  Evaluation  Society
     Newsletter, 4(4),  November  1979.   10 p. (Sees. Ill, 114,
     and 301(a)  of  the  Clean Air Act, as amended (42 U. S. C.
     7411, 7414, and 7601(a))).

16.  Steinsberger,  S.  C.  (Entropy  Environmentalists,  Inc.).
     Unpublished results of NO   sample  stability  study.  June
     1987.                    x

17.  Siemer,   D.  D.  Separation of Chloride  and  Bromide  from
     Complex  Matrices  Prior  to Ion Chromatographic Determina-
     tion.  Analytical Chemistry.  52  (12):1874-1877,   October
     1980.

18.  Eubanks,   D.  R.,  and   J.   R.   Stillian..  Care  of  Ion
     Chromatography  Columns.  Liquid Chromatography.  2 (2):74,
     1984.

19.  Hamil,  Henry  F. et. al.  The Collaborative Study  of
     Methods 5, 6, and 7 in Fossil Fuel  Fired Steam Generator
     Final Report, EPA-650/4-74-013, May 1974.

20.  Hamil,  H. F.,  and R. E. Thomas.   Collaborative  Study  of
     Method  for the Determination of Nitrogen  Oxide  Emissions
     from    Stationary   Sources    (Nitric    Acid    Plants).
     EPA-650/4074-028, May 1974.

21.  Hamil,  Henry F.  Laboratory and Field Evaluations  of  EPA
     Methods 2, 6,  and  7.   Final  Report,  EPA  Contract  No.
     68-02-0626,   Southwest  Research Institute,  San  Antonio,
     Texas, October 1973.
o
                                                              O

-------
                                                  Section No.  3.14.12
                                                  Date July 1,  1986
                                                  Page 1
12.0  DATA FORMS
    Blank data forms  are  provided  on  the  following pages for the
convenience of the  Handbook user.  Each blank form has the customary
descriptive title centered at the top  of  the  page.   However,   the
section-page  documentation in the top right-hand corner of each page
has  been  replaced with a number in the lower right-hand corner that
will  enable  the  user to identify and refer to a similar  filled-in
form in a text section.  For example, Form M7A-1.2 indicates that the
form is Figure 1.2 in  Section  3.14.1  of  the  Method  7A  section.
Future  revisions of these forms, if any, can be documented by  1.2A,
1.2B,  etc.   Eleven of the blank forms listed below are included  in
this section.  Four are  in the Method Highlights subsection as shown
by the MH following the form number.
3.1 (MH)

3.2 (MH)

4.1A AND 4.IB


4.2A and 4.2B


4.3 (MH)

5.1 (MH)

5.4


6.1A and 6.IB


8.1
Title

Procurement Log

Analytical Balance Calibration Form

Analytical Data Form for Analysis of
Calibration Standards

Pretest Sampling Checks

Pretest Preparations

Nitrogen Oxide Field Data Form (English
and metric units)

NO  Sample Recovery and Integrity Data
Form (English and metric units)

On-site Measurements

Posttest Operations

Analytical Data Form for Analysis of
Field Samples

Nitrogen Oxide Calculation Form  (English  and
metric units)

Method 7A Checklist to be Used by Auditors

-------
                                 PROCUREMENT LOG
Item description

fity.

Purchase
order
number

Vendor

Date
Ord.

Rec.

Cost

Disposition

Comments

                                                    Quality Assurance  Handbook  M7A-1.2
o
o
o

-------
               ANALYTICAL BALANCE CALIBRATION FORM
Balance name
Number
Classification of standard weights



Date

0.5000 g

1.0000 g

10.000 g

50.0000 g
i
100.0000 g

Analyst

                                  Quality Assurance Handbook M7A-2.1

-------
      ANALYTICAL  DATA  FORM FOR  ANALYSIS OF CALIBRATION STANDARDS
 Plant

 Date
             Location

             Analyst
 Was an integrator used?
yes
        no
o
Was the intercept (I) used for calculations? yes no
Were all points within 7 percent of calculated value? yes
Sample
Identifier
Std 1
Std 2
Std 3
Std 4
Std 5
Sample
Mass
(VS NO,,)
25
50
100
150
250
Integrator Response
or Peak Height (mm)
H
1





2





3





Avg





Predicted
Sample Mass
(yg NO,)





no
Deviation
(%)





Predicted Sample Mass using Least  Squares to Calculate  Calibration Factor (S)
  with Zero  Intercept
s . SIHI •
-iZ*
S_ v

{
s =
i- S2H2 + S^H^ + S^ + S5H5
H2 + H2 + R2 + H2
X ) + ( )( ) * ( )(

>2 * < >2 * < >2 • i
yg N0_/mm


>2 . i )2

                                                                             O
   Predicted Sample Mass (yg N0_)

                         \ *   /
   V g NO-  = H x S = (
         d.
                              Equation  2-1
Predicted  Sample Mass using Linear Regression to Calculate Calibration Factor
  and Non-Zero Intercept (I)

    y =  mx + b; m = 	
                                               (S)
        m
                  m
    y =  H;  and b = I (Intercept)  = 	

   Predicted Sample Mass (yg N0?)

    yg N02  = S(H - I)

    yg NO-  at 25 yg standard = 	(
                               Equation 2-
                                     Quality Assurance  Handbook M7A-2.3
                                                O

-------
  Plant
  Sample location
  Operator 	
 NITROGEN OXIDE FIELD DATA FORM (ENGLISH UNITS)
	  City 	
                        Date
                         Barometric pressure (P.  )
in.  Hg
Sample
number

Sample
point
location

Sample
time
24-hr

Probe
temperature ,
°F

Flask
and valve
number

Volume
of flask
and valve (Vp),
ml

Initial pressure
in. Hg
Leg R.±

Leg Bi

Pi3

Initial temperature
°F(ti)

°R(V±)b

     bar
Ti
                                                          Quality Assurance  Handbook M7A-4.1A

-------
   Plant
   Sample location



   Operator 	
 NITROGEN  OXIDE FIELD DATA  FORM (METRIC UNITS)


	  City	



                         Date
                         Barometric pressure (P.   )
                                              Dar
                                  mm Hg
Sample
number

Sample
point
location

Sample
time
24-hr

Probe
temperature,
°C

Flask
and valve
number

Volume
of flask
and valve (V_) ,
ml
«
Initial pressure
in. Hg
Leg AL

Leg B±

*ia

Initial temperature
°C(ti)

OKCS^)*

 '< = p
      bar
DT± = t± + 273°C.
   o
                        o
Quality Assurance Handbook M7A-4.
o

-------
         NO  SAMPLE RECOVERY AND INTEGRITY  DATA FORM (ENGLISH  UNITS)
    Plant                                  Date
    Sample recovery personnel
                                          Barometric pressure,  (P,   )
                                                                                 in. Hg
    Person with direct responsibility for recovered samples
Sample
number

Final pressure,
in. Hg
Leg Af

Leg B£

V

Final temperature,
°F (tf)

°R (Tf)b

Sample
recovery
time,
24-h

Liquid
level
marked

Samples
stored
in locked
container

p  =
          -  
-------
              N0x SAMPLE RECOVERY AND INTEGRITY DATA FORM (METRIC UNITS)
           Plant                                  Date
          Sample recovery personnel
                          Barometric pressure,  (P,  )
                                                                                      mm Hg
          Person with direct  responsibility for  recovered samples
Sample
number

Final pressure,
mm Hg
Leg Af

Leg Bf

*fa

Final temperature,
°C (tf)

°K (Tf)b

Sample
recovery
time,
24-h

Liquid
level
marked

Samples
stored
in locked
container

         - p
         - p
            bar
- (A,
Bf)
273°C.
       Lab person with direct responsibility for recovered samples
       Date recovered samples received 	  Analyst 	
       All samples identifiable? 	
       Remarks
                      All liquids at marked level?
       Signature  of lab sample trustee
o
                          o
                                                           Quality Assurance Handbook M7A-4.2B
                                                      o

-------
        ANALYTICAL  DATA FORM.FOR ANALYSIS OF  FIELD  SAMPLES
  Date samples received
  Plant
                                    Date samples analyzed
                                             Run number(s)
  Location
  Calibration factor (S)
  Reagent blank values:
                             1st,
Analyst 	
Intercept (I), if applicable
   2nd, 	 Avg
1
1
1

Field
Sample
Number





Analysis
Number







Instrument
Response
(mm)









Mean
Instrument
Response
(mm)




Deviation
(yg N02)
Mean

Instrument
Response
Blank
Corrected
(H)
i








Dilution
Factor
(F)






Mass of
Field
Sample
(ve N02)



Deviation of two samples, (%) = 100 x
Mass of field  sample
  without intercept
  (Vg N0) --
Mass of field  sample
  with intercept
                             = 100
                                               (must be less than
                             = S (H -  I)  F
                                   Quality Assurance Handbook M7A-5.4

-------
          NITROGEN OXIDE CALCULATION FORM (ENGLISH UNITS)




                           Sample Volume



    V, =         ml, P, =     .      in. Hg,  T,. =       °R
     i   —~ ^ — —      £__—_- —          £   __ — —


    P± =	.	in. Hg,  T± =	°R
                                                                   O
   V   =17.64 (V, - 25)  /If _ li 1 =         ml
    SC           I        I „,    rp     ____

                           lf   i
                                                       Equation 6-1
                        Sample Concentration


(No Intercept Used)


    H =	.	mm,  S =	vg/mm,


    F =	_,  V   =	ml


                                                       Equation 6-2


    C = 6.243 x 10"8 HSF x 10  =     .      x 10~5 Ibs N00/dscf
                        V
                         sc
                                                                   O

(With Intercept Used)


    H =	.	mm, I =	.	mm, S =	vg/mm,


    F "	'  vsc "	ml

                                                       Equation 6-3

    C = 6.243  x 10"8 (""DSP x 10  =     ^     x 1Q-5 lbs N0 /dscf

                           Vsc       --   --




                    Sample Concentration in ppm


                        ,                              Equation 6-4
    ppm N00 =  8.375 x 10  C =         ppm NO0
          ^                   — — — —       £
                                 Quality Assurance Handbook M7A-6.1A
                                                                  O

-------
           NITROGEN OXIDE CALCULATION FORM  (METRIC UNITS)





                           Sample Volume        • -; ••'•"




    Vf =	ml, Pf =	. _ mm Hg, Tf  =	. _ °K



    P. =       .mm Hg, T. =      .   °K
     4.   —~ ~— —~ """         Jl   *"~ ~~ ~-  —


                                                       Equation  6-1
>   /!«_i
   IT    T
   \T£   Ti
   Vsc = °-3858 (Vf - 25)  |^f _ li.) =	. ml
                        Sample Concentration



(No Intercept Used)



      H =  _ _. _ _ mm,   S = _ _ _ _ yg/mm



      F =	,  Vsc =	ml



                                                       Equation 6-2



      C = HSFVX 10  = _. 	 x 103 mg N02/dscm

              sc





(With Intercept Used)



    H =     .      mm, I =     .      mm,  S =         yg/mm,
    F =      ,  V             ml
        — — —   sc   — — — —
        (H-I)SF x 104 .   _       x 1Q3 mg N0 /dscm



           Vsc          ~
                                                       Equation 6-3
                    Sample Concentration in ppm





                                                       Equation 6-4



    ppm NO2 = 0.5228 C = _ 	 ppm NO2







                                 Quality Assurance Handbook M7A-6.1B
                                                 - / ?•>'

-------
METHOD 7A  CHECKLIST TO  BE USED BY AUDITORS
                                                               o
Yes
No
Comment
     Presampling preparation


     1.    Plant operation parameters variation

     2.    Calibration of the flask and valve volume	three
          determinations

     3.    Absorbing reagent preparation
              On-site measurements

     4.    Leak testing of sampling  train

     5.    Preparation and introduction of absorbing solution
          into sampling flask
                  Postsampling                       :
           (Analysis and Calculation)

     6.    Control sample analysis

     7.    Sample aliquotting techniques

     8.    Ion chromatographic technique

           a. Preparation of standard nitrate samples
              (pipetting)
           b. Calibration factor (+_ 7 percent for all
              standards)
           c. Duplicate sample values within 5 percent
              of their mean
           d. Adequate peak separation
                                                                               O
                      9. Audit results
                         10%)
          a. Use of computer program
          b. Independent check of calculations
                    Comments
                       Quality Assurance Handbook M7A-8
                                                                             •o

-------
                                          Section No. 3.15
                                          Date April 16, 1986
                                          Page 1
                       Section 3.15

       METHOD 7D - DETERMINATION OF NITROGEN OXIDE
            EMISSIONS FROM STATIONARY SOURCES

   (Alkaline-Permanganate - Ion Chromatographic Method)
                         OUTLINE


                                                    Number of
       Section                      Documentation      pages

SUMMARY         ~<                        3^15           3

METHOD HIGHLIGHTS                        3.15           8

METHOD DESCRIPTION

   1.  PROCUREMENT OF APPARATUS
       AND SUPPLIES                      3.15.1        18

   2.  CALIBRATION OF APPARATUS          3.15.2        21

   3.  PRESAMPLING OPERATIONS            3.15.3         6

   4.  ON-SITE MEASUREMENTS              3.15.4        10

   5.  POSTSAMPLING OPERATIONS'           3.15.5        13

   6.  CALCULATIONS                      3.15.6         5

   7.  MAINTENANCE                       3.15.7         .3

   8.  AUDITING PROCEDURES               3.15.8         6

   9.  RECOMMENDED STANDARDS FOR
       ESTABLISHING TRACEABILITY         3.15.9         1

  10.  REFERENCE METHODS                 3.15.10        9

  11.  REFERENCES                        3.15.11        2

  12.  DATA FORMS                        3.15.12       13

-------
                                              Section No. 3.15
                                              Date April 16, 1986
                                              Page 2
                             SUMMARY
     For  EPA Method 7D  ,  an integrated,  metered  sample  is  ex-
tracted via a heated probe postioned at a point  within  the duct
or stack.  The sample   is passed through a series of 3 restricted
orifice impingers each  containing an absorbing solution of sodium
hydroxide (NaOH) and potassium  permanganate (KMnO.).  The absor-
bing solution reacts with nitrogen oxides  in_the effluent gas to
form nitrate ion, N03~,  and nitrite ion, NO2~.  Nitrogen  oxides
(NO  ) are the sum of nitric oxide (NO) and nitrogen dioxide (NO,,)
whi^h are usually 19 to 1 by  weight in the emission stream.  Tfie
collected sample is allowed to sit for 36 hours prior to analysis
in   order  for   the  N02~  to  react  completely  to NO3~.   Ion
chromatography  is  then  used  to  quantify  the  NO3~  which is
functionally  related   to the NO  concentration of tne  effluent
sample.
    The absorbing solution also  reacts with carbon dioxide, C02,
in the effluent sample.  Therefore, EPA  Method  3 determinations
of  C02  must be conducted with Method 7D in order to correct the
Method 7D volumetric data for the volume of C02 absorbed.
    Ammonia,  NHo/  interferes  with  Method  7D  by causing  NO
results  to  be  biased high.  Method 7D results can be corrected
for the bias using data from concurrent determinations of
                                                                   []
                                                                   V __ /
    Collection  of  the NO is presumed  to  involve  oxidation  -
reduction reactions in which  the  NO is oxidized sequentially to
N00  and then to NO,,".   The  half reactions for the formation of
                   J
Mn04~ + 2H20
                   3e
    3NO + 60H~ = 3N02~ + 3H20

and the overall reaction is:

    3NO + MnO ~ + 20H~ = 3NO
             4              2
                              + 40H

                              + 3e~
                                 MnO0 + H0O
                                    22
The half reactions for the formation of N03~ are:

    3N02~ + 6OH~ = 3N03" + 3H20 + 6e~
2MnO
         4H2O
                    6e" = 2Mn0
        f Jt  *  ^**4^*^/  • W v3    
-------
                                              Section No. 3.15
                                              Date April 16, 1986
                                              Page 3

     NO  + MnO4~  » N03~  + Mn02                         Reaction S-7

     The rate  of the reaction of NO to N02~ is controlled  by  the
solubility  of  NO.    It  takes  approximately  36 hours for  the
reaction  of  N02~ to  N03~  to  reach  completion;  the  factors
controlling this reaction are unknown.

     Absorption  of  N02  is  also presumed to involve  an  oxida-
tion-reduction  reaction.   In contrast  to  NO,  N02  is  rather
reactive; thus, it is  reasonable to show N02 reacting directly to
N03~.   The half reactions are:

     3N02 + 6OH~ = 3NO3" + 3H20 + 3e~                 Reaction S-8
    MnO4  + 2H2° + 3e  = Mn°2 + 4OH                  Reaction S-9

and the overall reaction is:

    3NO2 + MnO4~ + 2OH~ = 3N03~ + Mn02 + H2O        Reaction S-10

    The_ absorption of CO2  involves the simple acid-base reaction
with OH~ to form bicarbonate ion, HCO3~:

                   CO2 + OH~ = HCO3"                Reaction S-ll

In the strongly basic absorbing  solution,  the  bicarbonate  ion
reacts further to carbonate ion, CO3~:

            HC03~ + OH~ = H20 + C03=                Reaction S-12

    Method 7D  is  applicable  to  the measurement of NO  emitted
from sources in the following categories:

    (a) fossil-fuel-fired steam generators subject to 40 CFR
        Part 60, Subpart D;

    (b) electric utility steam generating units subject -to 40 CFR
        Part 60, Subpart Da; and
                                                            >
    (c) nitric acid plants subject to 40 CFR Part 60, Subpart G.

    It may be used as an alternative to Method 7 [as  defined  in
40 CFR Part 6O.8(b)] to determine compliance if the stack concen-
tration is within tHe analytical range.  The lower limit  of  de-
tectability (with NO  defined as NOO is approximately 13 mg N02/
m  (7 ppm N02) when sampling is conducted at a flow  rate  of 500
cc/min for 1 hour.  The method's upper  analytical  limit has not
been  established; however, results  of  field  evaluations  have
shown that NO  can be collected  quantitatively at concentrations
of 1,782 mg N62/m  (932 ppm N02) when sampling  is conducted at a
flow rate of 500 cc/min for 1 nour.

-------
                                              Section No. 3.15
                                              Date A
                                              Page 4
Date April 16, 1986 S~"\
    The method description which  follows is based on the method
that was promulgated on September 27, 1984.

    Section 3.15.10  contains a copy of Method 7D, and blank data
forms are provided in Section 3.15.12  for the convenience of the
Handbook user.
                                                                  o
                                                                   o

-------
                                              Section No. 3.15
                                              Date April 16, 1986
                                              Page 5
                        METHOD HIGHLIGHTS
    Section 3.15 contains the required procedure for sampling and
analyzing  emissions  of  nitrogen oxides from stationary sources
using Method 7D.   For the method,  an integrated sample is taken
from  a  point  in  the  duct  or  stack  using  a  heated  probe
constructed  of boirosilicate glass, stainless steel,  or  Teflon?
The effluent sample stream is passed through  a  series  of three
restricted orifice impingers,  each  containing  200 ml of a 4.0%
(w/w)  KMn04  and  2.0%  (w/w) NaOH  solution,  termed  "alkaline
permanganate  solution."   The  alkaline  permanganate   solution
quantitatively removes NO ,  C02,  and SQ2 from the effluent sample
stream and converts these to ions: N02  and NO3~, CO3 , and S0.~,
respectively.   Sampling  is  conducted  at  a measured flow rate
between 400 and 500 cc/min  for  60  minutes.   The measured flow
rate is on a moisture- and C02-free basis, and consequently, when
the method is applied to effluents from combustion processes, the
measured flow rate will be less than the sampling flow  rate.  In
addition, sampling  for  C02  must be conducted using Method 3 in
conjunction  with  Method 7D in order to correct  the  volumetric
data for the volume of CO~ absorbed.

    After acquisition, the sample is allowed to sit for a minimum
of 36  hours  to  ensure  that  the  NO^"" has been quantitatively
reacted to N03~.  Sample preparation entails destruction  of  the
excess  permanganate  and  filtration  of  the  solid,  manganese
reaction  product, manganese dioxide  (MnO2).   NO   as  N03~  is
quantified using ion chromatography (1C).

    Ion chromatography is a relatively recent analytical develop-
ment.   The  reader  is  referred  to the literature for detailed
descriptions  of the subject. ~    Small, et al.,  developed  the
technique using the principles of ion exchange chromatography and
conductimetric  detection.  Previous attempts to use this type of
detection  were  unsuccessful  because  of  the presence  of  the
background electrolyte used for elution  of  the  ionic  species.
Small, et al., used a novel combination of resins to separate the
ions of interest and neutralize the eluent from the background.

    The aqueous sample is  introduced  into a fixed-volume sample
loop by  using  a  plastic syringe.  Once injected, the sample is
carried through a separation column at  different rates according
to  their  relative  affinities for the resin  material  and  are
therefore separated  into discrete bands.  The separated ions are
then  passed through a post-separation  suppressor  device  which
converts the  eluent  ions into a less conducting weak acid while
converting the analyte ions into a highly conducting  form.  This
permits  the  use of a conductivity  cell  as  a  very  sensitive
detector of all ionic species.
                     12
    Gjerde,  et  al^.,    described a modified ion chromatographic
method that eliminates the need  for a suppressor device.  Anions
                                                  .-n

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o
                                              Section No. 3.15
                                              Date April 16, 1986
                                              Page 6

 are  separated on a column containing an anion-exchange resin with
 a  low  exchange capacity.  Because of the  low  capacity,  a  very
 dilute solution of an aromatic organic  acid  salt may be used as
 the  eluent.  The conductance of the eluent  is  sufficiently  low
 that no suppression is needed.

     For Method 7D, either suppressed or non-suppressed  1C may be
 used.   The  basic  ion  chromatograph  will  have the  following
 components:

     (a)  sample injection device,

     (b)  anion separation column,

     (c)  anion suppressor column, either packed bed or fiber type
         (not required for non-suppressed 1C),

     (d)  conductivity detector, and

     (e)  recorder.

     The critical aspects of the method are (a) the neasurement of  —,
 the  gaseous  sample  volume, and  (b)  the  preparation  of  the f  ]
 calibration  standards  for  the ion chromatograph.  Analysts are \	/
 advised to observe specified procedures carefully at these points
 of   the  method.   Analysts  performing the method should be well
 trained in the use of the ion chromatograph.

     Collaborative testing  has  been  performed for Method 7D and
 the  results exhibit accuracy and  precision  similar  to  that of
Method 7.

     The approporiate  blank data forms at the end of this section
may  be  removed  from the Handbook and used in the pretest,  on-
 site,  and in posttest operations. • Each  form  has  a subtitle to
 assist the user in finding a similar filled-in fom in "the method
description.  On the blank and filled-in forms, the items/ paran-
eters  that can  cause  the most significant errors are designated
with an asterisk.

1.  Procurement of Apparatus and Supplies
    Section  3.15.1 (Procurement of Apparatus and Supplies) gives
specifications,  criteria, and design features  for  the  required
equipment and materials.  The sampling apparatus of Method 7D has
design features similar to those of Method 6.  Section 3.15.1 can
be  used  as  a guide  for  procurement  and  initial  checks  of
equipment  and  supplies.  The activity matrix (Table 1.1) at the
end of the section is a summary of the  details given in the test
and can be used as a quick reference.

2.  Pretest Preparations
    Section3.15.2(Calibration  of  Apparatus)  describes  the
  O

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                                              Section No. 3.15
                                              Date April 16,  1986
                                              Page 7

required calibration procedures and considerations for the Method
7D sampling  equipment (essentially the same as Method 6) and for
the  ion  chromatograph  (the  same  as for Method 7A).  Required
accuracies  for  each component are  also  included.   A  pretest
checklist (Figure  2.5,  Section 3.15.2) or a similar form should
be  used to summarize the calibration and other pertinent pretest
data.   The  calibration  section  may be removed along with  the
corresponding sections  from  the  other  methods and made into a
separate quality assurance  reference manual for use by personnel
involved in calibration activities.

    Section 3.15.3  (Presampling  Operations) provides the tester
with a guide for equipment and supplies preparation for the field
test.  With the exception of the preparation of certain reagents,
these are the same as for  Method  6  and  Method  3.   A pretest
preparation  form  (Figure 3.1, Section 3.15.3) can be used as an
equipment  checkout  and packing list.  The method of packing and
the use of the described packing  containers  should help protect
the equipment, but neither is required by Method 7D.

    Activity matrices for the calibration  of  equipment  and the
presampling operations  (Tables 2.1 and 3.1) summarize the activ-
ities.

3.  On-Site Measurements
    Section 3.15.4 (On-Site Measurements)  contains  step-by-step
procedures for sample collection and for sample recovery.  Sample
collection is similar  to  Method  6, with the exception that the
alkaline  permanganate  solution  is placed in restriced  orifice
impingers and the C02 content of the stack gas must be determined
to correct  the sample volume for the C02 removed by the sampling
train.   The  on-site  measurement checklist (Figure 4.4, Section
3.15.4) provides the tester with a quick method  of  checking the
on-site requirements.   Table 4.1 provides an activity matrix for
all on-site activities.

4.  Posttest Operations
    Section3.15.5("Post sampling Operations) gives the posttest
equipment procedures and a step-by-step  analytical procedure for
determination  of NO , expressed as N02-  The posttest operations
form (Figure 5.4, Section 3.15.5) provides some key parameters to
be  checked  by   the   tester  and  laboratory  personnel.   The
step-by-step analytical procedure description can be  removed and
made into  a  separate  quality  assurance  analytical  reference
manual  for  the  laboratory  personnel.   Analysis  of a control
sample  is  required prior to the analysis of the field  samples.
This  analysis  of independently prepared, known  standards  will
provide  the  laboratory  with  quality  control  checks  on  the
accuracy and precision  of  the  analytical  techniques.   Strict
adherence  to  the  Method  7D  analytical  procedures   must  be
observed.

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                                              Section No. 3.15
                                              Date April 16, 1.-.
                                              Page 8             (j

    Section  3.15.6  (Calculations) provides the tester with  the
required equations, nomenclature,  and significant digits.  It is
suggested that a calculator be used, if available, to  reduce the
chances of calculation error.

    Section 3.15.7 (Maintenance) provides the tester with a guide
for  a  maintenance  program.  This program is not required,  but
should reduce equipment  malfunctions.  Activity matrices (Tables
5.1,  6.1, and 7.1) summarize all postsampling, calculation,  and
maintenance activities.

5.  Auditing Procedure
    Section 3.15.8 (Auditing Procedures) provides  a  description
of  necessary  activities  for conducting performance and  system
audits.   The  performance  audit  of the analytical phase can be
conducted  using  audit samples supplied by the Quality Assurance
Division,  Environmental  Monitoring  Systems  Laboratory, U.  S.
Environmental Protection  Agency.  The data processing procedures
and a checklist for a systems audit  are  also  included  in this
section.   Table  8.1  is an activity matrix for  conducting  the
audits.

    Section  3.15.9  (Recommended  Standards   for   Establishing
Traceability) provides the primary standard to which the analysis x—v
data should be traceable.  The primary standard is sodium nitrate (   j
(NaNOg).                                                          V_y

6.  References
    Section 3.15.10 contains the promulgated  Method  7D; Section
3.15.11 contains the references cited  throughout  the  text; and
Section 3.15.12  contains  copies  of  data forms recommended for
Method 7D.
                                                                   o

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                                              Section No. 3.15
                                              Date April 16, 1986
                                              Page 9
Date
Meter box number
                     PRETEST SAMPLING CHECKS
                     (Method 7D, Figure 2.5)
Calibrated by
Dry Gas Meter*

Pretest calibration factor (Y) =
  average factor for each calibration run)
               (within 2% of
Rotameter

Pretest calibration factor (Y ) or setting
  (between 400 and 500 cc/minr.
Dry Gas Meter Thermometer

Was a pretest temperature correction made?
                res
no
If yes, temperature correction
        (within 3°C (5.4°F) of
         • ^_^_ •   f^Jf* / ^ f\ rt^^T1^ \ — -f?
  reference values for calibration and within 6 C (10.8 F) of
  reference values for calibration check).
Barometer

Was the pretest field barometer reading correct? 	yes 	no
 (within 2.5 mm (0.1 in.) Hg of mercury-in-glass barometer).
*Most significant items/parameters to be checked.

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                                             Section No. 3.15
                                             Date April  16, 1986
                                             Page 10
o
                      PRETEST PREPARATIONS
                     (Method 7D, Figure 3.1)
Apparatus check
Probe
Type liner
Glass
Stainless
steel
Other
Heated properly*
Leak checked
Filter
Glass wool
Other

Glassware
Restricted
orifice
impinger
Size
Type

Meter System
Leak-free pumps*
Rate meter*
Dry gas meter*
CO., Measurement
Orgat
Fyrite 	
Reagents
Water
Alkaline per-
manganate*
Silica gel
Other
Barometer
Drying tube
Acceptable
Yes







No







Quantity
required







Ready
Yes







No







Loaded
and packed
Yes







No







                                                                  O
*Most significant items/parameters to be checked.
                                                                   o
                                                     (n

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                                              Section No.  3.15
                                              Date April 16,  1986
                                              Page 11
                         ON-SITE MEASUREMENTS
                       (Method 7D, Figure 4.4)

Sampling
Impinger contents properly selected ,  measured, and placed in
  impingers?* 	

Impinger Contents/Parameters*
1st: 200 ml of KMn04/NaOH 	
2nd: 200 ml of KMn04/NaOH	
3rd: 200 ml of KMn04/NaOH 	
Drying tube: 6-16 mesh indicating type silica gel
Probe heat at proper level?* 	
Crushed ice around impingers? 	
Pretest leak check at 250 mm (10 in.) Hg?
Leakage rate? 	
Check of rotameter setting?
Probe placed at proper sampling point?
Flow rate constant at approximately 450 cc/min?*
CO2 concentration measured?* 	
Posttest leak check at 250 mm (10 in.) Hg?*
Leakage rate?* 	
Sample Recovery
Contents of impingers placed in polyethylene bottles?
Fluid level marked?*
Sample containers sealed and identified?*
*Most significant items/parameters to be checked.

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                                              Section No.  3.15
                                              Date April 16,  1986
                                              Page 12
o
                       POSTTEST OPERATIONS
                     (Method 7D,  Figure 5.4)
Reagents
Potassium  nitrate dried at 105 to 110°C for a minimum of 2 hours
before use? 	
Stock  standard '
-------
                                              Section No. 3.15.1
                                              Date April 16, 1986
                                              Page 1
1.0 PROCUREMENT OF APPARATUS AND SUPPLIES
    The procurement of appropriate apparatus and supplies enables
quality results  to  be  obtained  from Method 7D.  This  section
provides the user  with  information  which  complements  the two
sections of Method 7D, entitled  "Apparatus" and "Reagents."  The
information is offered in the form of guidance  and  includes the
following:

    o  Procedures for use  in checking whether apparatus conforms
       with  the requirements of the  Method  7D  and  corrective
       actions for when it does not (Table 1.1 at the end of this
       section summarizes  these  procedures  and  also  contains
       recommended corrective actions).

    o  Background information which can explain why specific  ap-
       paratus and  reagents  are  required,  and therefore, what
       limits may exist for alternatives or deviations.

    o  Practical information  pertinent  to the selection and use
       of apparatus and reagents.

    o  Safety considerations.

    Persons  responsible for the initial procurement of apparatus
and supplies may find a procurement  log helpful in ensuring that
all the necessary items are acquired  and  are  in  good  working
order.   A  procurement log can be used to record the descriptive
title of the equipment,  the  quantity,  an identification number
(if appropriate),  and  the  results  of  acceptance  checks.  An
example procurement  log  is shown by Figure 1.1, a blank copy of
this form is contained  in Section 3.15.12 for the Handbook user.
Calibration data obtained during acceptance checks also should be
recorded in a calibration log book; see Section 2.0.

1.1  Sampling Apparatus

    Figure 1.2 shows the sampling train for Method 7D.  It should
be noted that this sampling  train  is  very similar to that used
for  Method  6.   Several  of  the components and their  use' are
identical, including:

    o  Needle Valve
    o  Drying Tube
    o  Vacuum Pump
    o  Parts of the Metering System

This subsection addresses  the specifications needed for procure-
ment purposes  for  all  components  of  the  sampling  train and
associated apparatus.

1.1.1  Sampling  Probe  -  Method  7D  specifies   that  sampling

-------
Item description
                      Qty
Purchase
 order
 number
                       Vendor
                                                               Date
Ord.
Rec.
Cost
Disposition
Comments
              (/)
                            77A/5I
                      AAC,
      //&/&*

/f
                                                 U,
                                    Figure 1.1.   Example of a procurement  log.
                                                                                                         tJ o w
                                                                                                         CD pj CO
                                                                                                         IQ ft O
                                                                                                         (D 0) rt
                                                                                                             Z
                                                                                                             O
                                                                                                           M en
                                                                                                           vo •
                                                                                                           O3 I-1
 O
                            O
                                           O

-------
                                                    Section No.  3.15.1
                                                    Date April  16,  1986
                                                    Page 3
PROBE END PACKED.X
WITH GLASS WOOI*/*
,STACK WALL
RESTRICED ORIFICE IMPINGERS
                                                            SILICA GEL
                                                            DRYING TUBE
                Figure 1.2.    Method  7D sampling train.

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TM
                                              Section No.  3.15.1
                                              Date April 16,  1986
                                              Page 4

probes  are  to be constructed of borosilicate glass.  The method
also states that probes made  of either stainless steel or Teflon
are  acceptable.   Quartz probes (for example Vycorw) may be used
for sampling when effluent temperatures exceed 480  (900 F).

    The function of the probe is rather  simple:  to  transport a
representative effluent sample, cleaned of particulate matter, to
the impinger train.  To perform this function, the probe should:

   (a)   hold  a  filter  to remove particulate matter, including
         sulfuric acid mist;

   (b)   be  constructed  of a material that is unreactive toward
         N0x;

   (c)   be free from leaks;

   (d)   be sufficiently  long  to  enable samples to be acquired
         from the specified points(s) within the stack or duct;

   (e)   have provisions  for  being  heated  in order to prevent
         condensation of water vapor in the effluent sample; and

   (f)   be designed to connect  to  the  inlet  of  the impinger
         train.

The  three  materials identified above are unreactive toward NO .
The  appropriate length for the probe is determined primarily  By
its  intended  application  which  will  depend  upon  regulatory
requirements and the  dimensions  of  the stack or duct where the
measurements are to be made.

   Sampling probes are generally provided with electrical heating
systems consisting of a nichrome wire which is wrapped around the
probe.  The probe and heating system are, for protection,  placed
within a tightly fitting  tube,  referred  to  as  a sheath.  The
heating system should  be  capable  of preventing condensation of
water  vapor  in  the  effluent  sample  stream  during sampling.
Condensation is not desired, because water absorbs N02 and lowers
NO   results.   Additionally, if a stainless steel probe is used,
condensation will promote corrosion which shortens probe lifetime
and makes cleaning difficult.

   It  is  recommended  that probes be performance checked before
initial use in the field to  ensure that condensation can be pre-
vented.  The probe should first be visually checked for cracks or
breaks  and  then  checked  for leaks according to the  procedure
described in Section 3.15.3 of this  Handbook.   Then  the  probe
heating system should be checked as follows:

  1. Connect the probe (without filter) to the inlet of the pump.
  o
   o
    o

-------
                                              Section No. 3.15.1
                                              Date April 16, 1986
                                              Page 5

   2.   Electrically  connect and turn on the probe heater for 2 or
3  minutes.  If functioning properly,  it  will become warm to the
touch.

   3.   Start the  pump,  and  adjust the needle valve until a flow
rate of between 400 and 500 cc/min is achieved.

   4.   Check the  probe.  It should remain warm to the touch.  The
heater must be capable of maintaining the exit air temperature at
a  minimum of 100 C (212 F) under these conditions.  If it cannot,
the  probe  should  be  rejected.   Any probe not satisfying  the
acceptance check should be repaired, if  possible, or returned to
the supplier.

    The connection  between  the  probe's outlet and the impinger
train  may be a simple fitting or an additional length of tubing.
Any  connection should be leak-free.  In addition, the connection
should be constructed of borosilicate glass, stainless steel, or
Teflon™, and therefore, like  the probe be unreactive toward NO .
Lastly,  if tubing is used, provisions should  exist  to  prevent
condensation of water vapor upstream of the impinger train during
sampling.  A heating system for the connection is not required if
the probe's heating system can supply enough heat to the effluent
sample.

1.1.2  Restricted Orifice Impingers - The sampling train requires
the use  of  three  restricted  orifice  impingers  connected  in
series.  Figure 1.3  shows  one  of  these  irapingers,  which are
commercially available.
                                                               13
    Impinger  design  is  important  to obtain quality results.
The  restricted  orifice  impinger  is  specifically designed  to
promote  the  complete  collection of NO,  which   is  relatively
unreactive.  Two design features are important: (a) the length of
the liquid column, and (b) the size of the impinger's  stem  tip.
The  impingers  used  for  Method 7D are narrower than Greenburg-
Smith  impingers in order to provide a greater depth of  absorbing
reagent and, hence, to increase  the  reaction time of the sample
gas in the absorbing reagent.  Because of the narrow  openin.g  of
the  stem  tip,  the  effluent  sample  is  introduced  into  the
absorbing  reagent as smaller bubbles.  Smaller  bubbles  promote
the  reaction  of  NO  because of their greater surface-to-volurae
ratio  and thus, greater exposure to the absorbing reagent.

    Impingers  with  stem  tips restricted to less  than  1.5  mm
internal diameter are easily plugged  by  reaction products.  The
problem typically affects only the first impinger of the sampling
train  because: (a) most of the NO   and  CO2,  and  (b)  all  the
sulfur  dioxide,   if  present, are reacted rhere.   The  plugging
problem can be minimized by making the  length  of  the capillary
tubing as short  as practical.  Plugging also can be minimized by
keeping stem tips clean.   Reaction products in the stem  tips can

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DIMENSIONS: mm
         35

     CAPILLARY
     TUBING:
     1.5 I.D.
                                          Section No. 3.15.1
                                          ,-Date April 16, 1986
                                          Page 6
                              28/12
o
                                                                  o
      Figure  1.3.   Restricted orifice irapinger.
                                                                  O

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                                              Section No. 3.15.1
                                              Date April 16, 1986
                                              Page 7

be removed by immersion in either 3 percent  by  volume  hydrogen
peroxide solution  [3% (v/v) H^O..,  (aq)]  or  3M hydrochloric acid
solution [HC1 (aq)].  CAUTION!   Chlorine  (C12)  gas  is evolved
during the use of  the HC1; therefore, cleaning  operations should
be  conducted in a fume hood.  The H^O^ solution is identical  to
the absorbing solution used for Method 6.

    It is recommended that each  impinger upon receipt be checked
visually for  damage,  such as breaks or cracks, and for manufac-
turing flaws, such as poorly shaped connections.

    Other  nonspecified collection absorbers  and  sampling  flow
rates may be used, subject  to the approval to the Administrator,
but collection efficiency must  be  shown  to be at least 99% for
each  of  three  test runs and must be documented in the emission
test report.  For  efficiency testing, an extra absorber  must  be
added and analyzed separately  and  must not contain more than 1%
of the total NO .  Three  Greenburg-Smith design impingers may be
sufficient to provide adequate collection efficiency.

1.1.3  Vacuum Pump - The  vacuum  pump should'be capable of main-
taining a flow rate of approximately 400 to 500  cc/min  for pump
inlet vacuums up to 250 mm (10 in.) Hg with the pump outlet  near
standard pressure,  [i.e., 760 mm (29;92 in.) Hg].  The pump must
be leak free when  running and pulling a vacuum (inlet plugged) of
250 mm (10 in.) Hg.  Two types of vacuum pumps are commonly used:
either  a modified sliding fiber vane pump'or a  diaphragm  pump.
For safety reasons, the pump should be equipped with a three-wire
electrical cord.

    To check the pump for leaks, install  a  vacuum  gauge in the
pump inlet line.   Plug the inlet line, and run the pump until the
vacuum gauge reads 250 mm (10 in.) Hg of vacuum.  Clamp the  pump
outlet  line, and  turn off the pump; the  vacuum  reading  should
remain stable for  30 seconds.

1.1.4   Volume  Meter  -  The  dry  gas meter must be capable  of
measuring  total volume with an accuracy to within 2%, calibrated
at the selected flow rate (between  400 and 50O cc/min), and must-
be  equipped  with a temperature  gauge  (dial  thermometer,  or
equivalent) capable of measuring the gas temperature to within 3
C (5.4°F).

    A new dry gas  meter may be checked for damage visually and by;
performing  a calibration according  to  Section  3.5.2  of  this
Handbook.   Any  dry  gas meter that is damaged, behaves  errati-
cally, or does not give readings within +2% of  the selected flow
rate  for  each  calibration  run  is unsatisfactory.  Also  upon
receipt, the meter should be calibrated over a varying flow range
to see whether there is any effect on the calibration.

    Dry gas meters that are equipped  with  temperature compensa-

-------
                                              Section No.  3.15.1
                                              Date April 16,  1986
                                              Page 8
o
tion  must  be  calibrated  over the entire range of temperatures
that  the  meter  encounters under actual field conditions.   The
calibration must contain at  least  one  data  point at each 10°?
interval.  All temperatures that are to be used in the field must
be within 2% of the calibrated value.

    The wet test meter used to check the dry gas meter  should be
calibrated using the primary displacement  technique explained in
Section 3.5.2 of this Handbook.   The  wetgtest meter must have a
capacity of at least 0.0003 m /min (0.1 ft /min) with an accuracy
of +2%; otherwise at the higher flow rates, the water will not be
level and this possibly will result in an incorrect reading.

1.1.5  Rotameter - A rotameter,  or  its equivalent, with a range
of 0 to 1 L/min is used  to  monitor the sampling flow rate. The
rotameter is checked against the calibrated  dry  gas  meter with
which  it is to be used or against a wet test meter.   The  rota-
meter flow setting of about 450 cc/min should be determined.

    Changes in pressure, density, and viscosity of the sample gas
will affect the calibrated sample rate.   However, since sampling
is performed at a constant rate, which  need  not  be isokinetic,
these changes do not affect the sample volume measured by the dry X~N
gas meter.                           ^                           f   J

1.1.6  Needle Valve -  A  metering  valve with conveniently sized
fittings  is required in the sampling train to adjust and control
the sample flow rate.  It is recommended that the needle valve be
placed on the vacuum side of the pump.

1.1.7  Drying Tube - The drying tube should be packed  wi-th 6- to
16-mesh indicating-type silica gel, or  equivalent,  to  dry  the
sample gas and to protect  the pump and the meter.  A drying tube
can be made by filling a 10-mm polyethylene  tube with silica gel
and  packing glass wool in each end to hold the silicia  gel  and
protect the sampling system.  Plastic tubing can be  utilized  in
any  connections   downstream  of  the  impinger   train  without
affecting the sampling  results.   The  drying tube should have a
minimum  capacity  of 30 to 50 g of  silica  gel  and  should  be
visually checked before use for proper size and for damage.

    If the silica gel  has been used previously, it must be dried
at  175 C  (350 F) for 2 hours.  New silica gel may  be  used  as
received.   Other  types  of  desiccants  may  be used subject to
approval of the Administrator.
1.1.8   Metering System - For ease of use, the metering  system—
which contains  the  dry  gas meter, thermometer(s), vacuum pump,
needle   valve,  and rotameter—can be assembled  into  one  unit
(meter  box). After a meter box has been  either  constructed  or
purchased, then positive and negative pressure leak checks should
be performed.
 O

-------
                                              Section No. 3.15.1
                                              Date April 16, 1986
                                              Page 9

     The  positive  pressure  leak  check, similar to the procedure
described in Method  5   (Section  3.4)  of this Handbook, is per-
formed as follows:

     1.   Attach  rubber tubing and inclined manometer,  as shown in
Figure 1.3 of Section 3.4.1.

     2.   Shut off the needle valve, and apply positive pressure to
the  system  by blowing  into the rubber tubing until the inclined
manometer or  magnehelic gauge  reads from 12.5 to 17.5 cm (5 to
7 in.) H20.

     3.   Pinch  off  the tube,  and  observe the manometer for 1
minute.  A loss of pressure indicates a leak of the apparatus  in
the  meter box.

     After the   meter  box  apparatus has passed the positive leak
check,   then  the  negative  leak  check  should be performed  as
follows:

     1.   Attach  the vacuum gauge at the inlet to the drying tube,
and  pull a 250  mm (10 in.) Hg vacuum.

     2.   PincbNor^clamp the outlet of the flow meter.  This can be
accomplished by closing  the optional shutoff valve if employed.

     3.   Turn off the  pump.   Any  deflection noted in the vacuun
reading within  30 seconds indicates a leak.

     4.   Carefully release  the  vacuum gauge before releasing the
flow meter end.

     If either of these checks detects  a leak that cannot be cor-
rected,  the meter box must be rejected and/or  returned  to  the
manufacturer.

     The  dry gas meter must be equipped with a temperature  gauge
(dial  thermometer  or   equivalent).  It is recommended that upon
receipt this be checked visually for damage, such as dents  or  a
bent stem.  The thermometer should read within 3 C (5.4°F) of the
true  value  when  checked  at two different ambient temperatures
against  a mercury-in-glass thermometer  that conforms to ASTM E-l
No.  63C or 63F.  The  two  ambient temperatures used to calibrate
the  thermometer must differ by a minimum of 1O C (18 F).  Damaged
thermometers that cannot be calibrated are to be rejected.

     1.1.9   Barometer  -  A  mercury, aneroid, or other barometer
capable  of  measuring   atmospheric  pressure  to within  2.5  na
(0.1 in.) Hg may be used.  However, in many cases, the barometric
pressure  can be obtained from a nearby National Weather  Service
Station,  in  which case the station value (which is the absolute

-------
                                              Section No.  3.15.1
                                              Date April 16,  1986   —.
                                              Page 10             f  ^

barometric pressure)  should  be requested.  The tester should be
aware that the pressure is normally corrected to sea level by the
weather station; the uncorrected readings should be obtained.  An
adjustment  for  differences  in elevation of the weather station
and the sampling location is applied at a rate of -2.5 mm Hg/30 m
(-0.1 in. Hg/100 ft) of elevation increase,  or  vice  versa  for
elevation decrease.

    Accuracy  can  be  ensured  by  checking  the field barometer
against a mercury-in-glass barometer or  its  equivalent.   If the
field  barometer  cannot  be  adjusted to agree with the mercury-
in-glass barometer, it is not acceptable.

1.1.10  Vacuum  Gauge  - At least one 760-mm (29.92-in.) Hg gauge
is  necessary  to leak check the sampling train.   An  acceptable
vacuum gauge, when checked in a  parallel  leakless system with a
mercury U-tube manometer at 250-mm (10-in.) Hg vacuum, will agree
within 25 mm (1.0 in.) Hg.

1.2  Sample Recovery Apparatus

1.2.1   Wash  Bottles  -  Two 500-ml polyethylene or  glass  wash
bottles  are  needed  for  quantitative   recovery  of  collected
samples.  x/"""
                                                                   o
1.2.2   Storage Bottles - One 1-L polyethylene bottle is required  ^+-~s
to  store  each collected  sample.   An  additional  polyethylene
bottle is necessary to retain a blank for each absorbing solution
used in testing.   Wash  and  storage  bottles should be visually
checked for damage.  CAUTION:  Each storage bottle seal should be
checked prior to use to ensure that leakage will not occur.

1.2.3  Funnel  and  Stirring  Rods - The analyst may find a glass
funnel and glass  stirring  rods  are helpful in transferring the
absorbing reagent  to  and from the restricted orifice impingers.
The flow of absorbing reagent can be controlled  by pouring along
the glass stirring rod.

1.3  Apparatus for Sample Preparation and Analysis

1.3.1   Magnetic  Stirrer  with  Magnetic  Stirring  Bars  -  The
magnetic  stirrer  and stirring bars are used for the removal  of
excess permanganate ion.  The  stirring  bars  should be Teflon1"-
coated owing to the corrosiveness  of  the  alkaline-permanganate
solution.  Stirring  bars  having  dimensions  25 mm by 10 mm are
recommended.  Smaller stirring bars can be  expected  to  be less
efficient  because  of  the  resistance  offered by the absorbing
reagent, which is relatively viscous.
    Manual stirring  is  acceptable;  however,  being tedious and
laborious, it is not recommended.
                                                                   O

-------
                                              Section No. 3.15.1
                                              Date April  16,  1986
                                              Page 11

1.3.2  Filtering  Flask  -  One  filtering  flask having  a  500-ml
capacity is needed to filter the liquid  sample  after  the  excess
permanganate ion has been removed.

1.3.3  Buchner  Funnel  -  The  Buchner  funnel  is  used  with the
filtering flask for the filtering  operations.  A convenient size
funnel  is one with a 75-mm internal diameter.  The   analyst  may
wish to attach a section of Teflon™ tubing  to the  funnel's spout
in order to
-------
o
                                              Section No.  3.15.1
                                              Date April 16,  1986
                                              Page 12

1.3.9   Erlenmeyer  Flasks  -  Erlenmeyer  flasks having a 250-ml
capacity are used for operations involving  the removal of excess
permanganate ion in the samples.

1.3.10  Ion Chromatograph - An ion chromatograph (1C) is used for
analyzing the samples.  The instrument should, at a minimum,  have
the components described below.

    Columns  —The  1C  should be equipped with an ion separator
column capable of resolving nitrate ion (N03~)  from  sulfate ion
(SO."),   which   may   be   found   in   samples   acquired   at
fossil-fuel-fired  steam  generators.   In addition, it should be
capable of detecting and  resolving  nitrite  ion (N02~).   Either
suppressed  or  nonsuppressed  IC's  may  be  used  provided that
performance meets  the above criteria.  Suppressed IC's should be
equipped with an  acid  (H ) suppressor column in addition to the
anion separator column.  Suppressor columns (fiber preferred over
packed bed) are generally produced as proprietory items; however,
an acceptable  column  can be made using the resin available from
BioRad Company, 32nd and Griffin Streets, Richmond, California.

    Pump  -  The pump must be capable  of  maintaining  a  steady
eluent flow as required by the system.

    Flow  Gauges  -  These  must  be  capable  of  measuring  the
specified eluent  flow rate.  It is recommended that the gauge be
calibrated upon receipt.

    Conductivity Detector - It is recommended  that  the detector
be   calibrated according to manufacturer's procedures  prior  to
initial use.

    Recorder - It should be compatible with the output voltage of
the detector.

1.3.11  Analytical Balance -  One  analytical balance that weighs
to 0.1 mg and a set of Class-S  calibration  weights to check the
accuracy of the balance  (+0.3  mg) upon receipt are needed.  The
balance  should  be  serviced  or returned to the manufacturer if
agreement cannot be met.

1.4  Reagents  -  Unless otherwise indicated, it is intended that
all reagents  conform  to  the  specifications established by the
Committee on Analytical Reagents of the American Chemical Society
(ACS), where such  specifications  are  available; otherwise, use
the best grade available.

1.4.1  Sampling - For sampling, the following are needed.            -~

    Absorbing  solution  -  The absorbing solution is prepared by    V_x
dissolving40.0g potassium permanganate  (KMnO.)  and  20.0  g
o

-------
                                              Section No. 3.15.1
                                              Date April 16, 1986
                                              Page 13

 sodium  hydroxide   (NaOH)  in  940  ml  of water.  The solution's
 concentration  is   4.0 percent (w/w)  KMnO.,  2.0  percent  (w/w)
 NaOH.   CAUTION:  Extreme care should be taken  in  handling  the
 KMnO.  reagent  and the  absorbing  solution.  KMnO, is a strong
 oxidant  and  is  incompatible with substances containing  carbon
 such  as paper, fabric, and human tissue.  It is recommended that
 eye protection be worn  when  handling  the  absorbing  solution.
 Skin  exposed to the absorbing solution  should  be  washed- with
 plenty of water and until the exposed area  no  longer exhibits a
 soapy feeling.

    Water -  Water  should  be  used  which  conforms  with  ASTM
 specification  D1193-82, Type III.  Type III water is prepared by
 distillation, ion exchange,  reverse  osmosis,  or  a combination
 thereof,  followed  by polishing with a 0.45 ym  membrane  filter.
 The specifications  for Type III water are shown below.

        Specifications for ASTM D1193 - 82, Type III Water


          Total matter, max., (mg/L)            1.0

          Electrical conductivity, max.,        1.0
           (umho/cm) at 25 C

          Electrical resistivity, min.,         1.0
           (ymho/cm) at 25 C

          pH at 25°C                        6.2 to 7.5

          Minimum color retention time          10             '
           of KMnO4, (min)

          Maximum soluble silica, (vg/L)        10

Note: Mention of "water"  anywhere  in this Section (3.15) refers
to ASTM D1193-82, Type III Water as described  above.   By  using
water  from  the  same source for  making  reagents,  calibration
standards, and eluents for the ion chromatograph, the presence of
trace  quantities   of  nitrate in  the  water  will  be  negated.
Therefore, a  water blank  correction  is  not  necessary in the
development of the  calibration curve.

1.4.2   Analysis  -  For analysis,  the  following  reagents  are
required.
                                                                ••• y'
    Water - See Subsection 1.4.1 above.                          *

    Hydrogen Peroxide - Five (5) percent  (v/v) hydrogen peroxide
 (H?O2) is used which is prepared by mixing 1 part  30% (v/v) H^O,
with 5 parts water.

-------
                                              Section No. 3.15.1  S~\
                                              Date April 16, 1986 (   )
                                              Page 14             v—/

    Reagent Blank - The reagent- blank may  be prepared by dissol-
ving  2.4  g KMnO4 and 1.2 g NaOH in 96 ml water.  Alternatively,
the blank may be prepared by diluting  60  ml  of  the  absorbing
reagent to 100 ml using water.

    Potassium Nitrate (KNO-) Standard Solution  -  The  following
procedure is observed to prepare the KN03 standard solution.

   1. Dry an-adequate amount of KNO«  at 110°C for about 2 hours;
then transfer to a desiccator, and allow to  cool  to  laboratory
temperature.

   2. Using an analytical balance, accurately  weigh 9 to 10 g of
the dried KN03 to the nearest 0.1 mg.

   3. Transfer the KN03 to a suitable  container,  such as a bea-
ker, dissolve the KN03 in water, and transfer all  of  the   KNOo
solution to a 1-L volumetric flask.

   4. Dilute the KN03 solution to the 1-L mark with water.

The  N03~ concentration_of the standard  solution  is  calculated
from the mass of KN03 using the following relationship:

    N03~              Mass of KNO /"'>3
Concentration   =        (g)
'q/10  yg . L \/ 62.01 g/mol NO "\
 yg . ml  /yiOl.10 g/mol KN03/
Method  7D states that the KN03 standard solution is stable for 2
months  without  preservative  at laboratory conditions.   Novice
analysts should note that certain microbes feed on N03~" solutions
with the consequence for Method 7D being that NO  results will be
biased  high.   For this reason,  standard  solutions  should  be
disposed of after 2 months.

    Eluent  Solution  -  For  IC's   involving   the   suppressed
technique.,,  an  eluent  solution  being  3  x  10~  M NaHCO3  and
2.4 x 10     M   Na2C03   has   proved  adequate  for  Method  7D
applications.   This  eluent is prepared by taking 1.008 g NaHCO-
and 1.018 g Na2C03 and dissolving them in 4 L water.

    Other eluents may  be  used provided that they are capable of
resolving N03~ from SO.~ and other  ions  which may be present in
samples.

    Quality Assurance Audit Samples  -  Quality  Assurance  Audit
Samples are required to be analyzed  in  conjunction  with  field
samples.   The  audit  samples  for Method 7D are essentially the
same as those described in Method  7, Section 3.3.9.  Because the
analytical range for Method 7D  differs  from  that for Method 7,
analysts requesting audit samples should  specify that samples be
applicable to Method 7D.                              .       •   ,

-------
                                                               Section No.  3.15-1
                                                               Date April 16,  1986
                                                               Page 15

         Table  1.1.  ACTIVITY MATRIX FOR PROCUREMENT OF APPARATUS AND SUPPLIES
Apparatus  and
  supplies
Sampling probe
 with heating
 system
Restricted
 orifice
 impingers
Vacuum pump
  Acceptance limits
Capable of maintaining
100°C  (212°F) exit
air at flow rate of
500 cc/min
Standard stock glass;
ensure that dimensions
conform with specifi-
cations
Capable of maintaining
flow rate of AOO to
500 cc/min; leak free
at 250 mm (10 in.) Hg
Dry gas meter
Wet test meter
Rotameter
Drying tube
Capable of measuring
total volume within
2% at a flow rate of
500 cc/min
Capable of measuring
total volume within
2% at a flow rate of
500 cc/min
Within 5% of manufac-
turer's calibration
curve (recommended)
Minimum capacity of
30 to 50 g of silica
gel
Frequency and method
   of measurement
Visually check and
run heating system
checkout
Visually check upon
receipt for breaks
or  leaks
Check upon receipt
'for leaks^ and^capacity
Check for damage upon
receipt, and calibrate
(Sec. 3.15.2) against
wet test meter
Upon assembly, leak
check all connections,
and check calibration
by liquid displacement
Check upon receipt for
damage, and calibrate
(Sec. 3.15.2) against
wet test meter
Visually check upon
receipt for damage and
proper size
Action if
requirements
are not met
Repair, or
return to
supplier
Return to nanu-
facturer
As above
Reject if dam-
aged, behaves
erratically, or
cannot be
properly adjusted
As above
Recalibrate, and
construct a new
calibration curve
Return to supplier
(continued)

-------
                                                               Section No.  3.15.1
                                                               Date April 16,  1986
                                                               Page 16
Table 1.1 (continued)
                                                                  o
Apparatus and
  supplies
  Acceptance limits
Frequency and method
   of measurement
Action if
requirements
are not met
Thermometers
Within 1°C (2°F)
true value in the range
of 0 C to 25°C
(32° to 77°F)
for impinger and within
3°C (5.4°F) for
dry gas meter thermom-
eter
Check upon receipt for
damage (i.e., dents and
bent stem), and
calibrate (Sec. 3.15.2)
against mercury-in-
glass thermometer
Return to
supplier if unable
to calibrate
Barometer
Capable of measuring
atmospheric pressure
to within 2.5 mm
(0.1 in.) Hg calibrate
Check against mercury-
in-glass barometer or
equivalent (Sec. 3-5-2)
Determine cor-
rection factor,
or reject if
difference is
more than 2.5 m
o
Vacuum gauge
0 to 760 mm (0 to
29.92 in.) Hg range,
^25 mm (1.0 in.) Hg
accuracy at 250 mm
(10 in.) Hg
Check against U-tube
mercury nanometer
upon receipt
Adjust, or re-
turn to supplie
Wash bottles
Polyethylene or glass,
500-ml
Visually check for
damage upon receipt
Replace, or re-
turn to supplier
Storage
 bottles
Polyethylene, 1-L
Visually check for dam-
age upon receipt, and
be sure that caps seal
properly
As above
Pipettes and
 volumetric
 flasks
Glass, Class-A
Upon receipt, check for
stock number, cracks,
breaks, and manufac-
turer flaws
As above
Water
(continued)
Must conform to ASTM-
Dl193-82, Type III
Check each lot or spec-
ify type when ordering
As above
                                                                   O
                                                                  }
                                                                 I

-------
                                                               Section No.  3.15.1
                                                               Date April 16,  1986
                                                               Page 17
Table 1.1  (continued)
Apparatus and
  supplies
Stopcock
 grease
Analytical
 balance
Ion Chroma-
 tograph
  1.  Columns
  2.  Pump
  3.   Flow
      gauges
(continued)
  Acceptance limits
High vacuum, high temp-
erature chlorofluoro-
carbon grease
Capable of measuring
to +0.1 mg
1.  Capable of giving
nitrate ion peaks with
baseline separation
2.  Capable of deliv-
ering eluent at con-
stant and repeatable
flow rate
3.  Capable of giving
repeatable indications
of eluent flow rate
Frequency and method
    of measurement
Visually check upon
receipt
Check with standard
weights upon receipt
and before each use
1.  Check during
analyses
2.  Check during
analyses by monitor-
ing flow rate
3.  Check calibration
and repeatability
upon receipt
  Action if
  requirements
  are not net
Return to
supplier, and
note in procure-
ment log
Replace, or
return to manu-
facturer
                                                             i
  1.  Consult opera-
tor's manual; re-
generate sup-
pressor column;
clean separator
column; check
performance of
components below;
replace column(s)
if above actions
are unsuccessful

  2.  Consult opera-
tor's manual;
oil, clean, re-
repair, replace,
or return to man-
ufacturer; check
tubing of ion
chromatograph for
leaks or ob-
structions;
check flow neter
performance

3.  Consult oper-
ator's manual;
adjust, repair,
replace, or return
to manufacturer

-------
Table 1.1 (continued)
                                                               Section No.  3.15
                                                               Date April 16,  1986
                                                               Page 18
986Q
Apparatus and
supplies
4 . Conduc-
tivity
detector
5 . Recorder
Hydrogen per-
oxide
Potassium
nitrate
Sodium carbonate
Sodium bicarbon-
ate
Sodium hydroxide
Potassium
permanganate
Acceptance limits
4. Capable of giving
responses which can be
manually or electron-
ically integrated
within a precision of
5 percent
5- As above, if used
record responses for
manual integration
30# aqueous solution,
ACS reagent grade
ACS reagent grade
ACS reagent grade
ACS reagent grade
ACS reagent grade
ACS reagent grade
Frequency and method
of measurement
4. Calibrate accord-
ing to manufacturer's
instructions prior to
use
5- Check during
analyses
Check each lot, or
specify type when
ordering
As above
As above
As above
As above
As above
Action if
requirements
are not net
4. Consult opera-
tor's manual;
Repair, replace.
or return to
manufacturer
5- Consult opera-
tor's nanual;
adjust speed
Replace or return
to manufacturer

As above
As above
As above
As above
                                                                                  o

-------
                                              Section No. 3.15.2
                                              Date April 16, 1986
                                              Page 1
2.0  CALIBRATION OF APPARATUS
    Calibration of  the  apparatus  is  one of the most important
functions in maintaining data quality.  The  detailed calibration
procedures  included  in  this  section  were  designed  for  the
equipment specified in Method  7D  and  described in the previous
section.   Table  2.1  at the end of this section summarizes  the
quality  assurance  functions  for calibration.  All calibrations
should  be  recorded on standardized  forms  and  retained  in  a
calibration log book.

    The  calibration  procedures and considerations addressed  in
this  section  are  those which are unique  to  Method  7D.   The
sampling phase of Method 7D involves the use of equipment that is
essentially  the  same  as  that used for Method 6.  The analysis
phase  of  Method  7D entails the use of an ion chromatograph, an
instrument that also is used  for  Method  7A.  The Handbook user
should note  that:  (a) the standard used for Method 7A is sodium
nitrate  (NaNO,-,  while  for  Method  7D  the  standard  used  is
potassium nitrate (KNO^); and (b) sulfate ion (SO4~) peaks in ion
chromatograms  for  Method  7D will have  a  lesser  tendancy  to
overlap  and_ therefore  to  interfere  with nitrate (NO3~) peaks
because  SO."  will  exist  at  a  lower concentration because it
originates only from sulfur oxides in the effluent.

2.1  Metering System

2.1.1.  Wet Test Meter - The wet test  meter  must  be calibrated
and have the proper capacity.  For  Method 7D, the wet test meter
should have a capacity  of  at  least 1 L/min.  No upper limit is
placed  on  the capacity; however, the wet test meter dial should
make at least one complete revolution at the specified  flow rate
for each of the three independent calibrations.

    Wet  test  meters  are  calibrated by the manufacturer to  an
accuracy  of  +2%.   Calibration  of  the  wet test meter must be
checked initially upon receipt and yearly thereafter.

    The  following liquid positive displacement technique can  be
used to verify and adjust,  if necessary, the accuracy of the wet
test meter to +2%:

    1.  Level the wet test  meter by adjusting the legs until the
bubble on the level located on the top of the meter is centered.

    2.  Adjust the water volume  in the meter so that the pointer
in the water level gauge just touches the meniscus.

    3.  Adjust the water manometer to zero by moving the scale or
by adding water to the manometer.

    4.  Set up the apparatus and calibration  system  as shown in
Figure 2.1.



                                              / -V- 3

-------
                                              Section NoJr3;15.2
                                              Date April 16,  1986
                                              Page 2
o
               MANOMETER
      THERMOMETER
AIR INLET
                                   WATER
                                   LEVEL
                                   GAUGE
                                   OUT
                                                      VALVE
                                                      200O-ml LINE
                                                         TYPE-A
                                                         VOLUMETRIC
                                                         FLASK
                                                                       O
Figure 2.1.   Calibration check  apparatus for wet test  meter.'
                                                                        O

-------
                                              Section No. 3.15.2
                                              Date April 16, 1986
                                              Page 3

        a.   Fill the  rigid-wall  5-gal  jug with water to below
             the air inlet tube.  Put water in  the  impinger  or
             saturator,  and  allow  both  to equilibrate to room
             temperature (about 24 hours) before use.

        b.   Start  water  siphoning  through  the  system,   and
             collect the  water  in a 1-gal container, located in
             place of the volumetric flask.

    5.  Check -operation of the meter as follows:

        a.   If the manometer is reading  <10  mm  (0.4 In.) H2O,
             the meter is in proper  working condition.  Continue
             to step 6.

        b.   If  the manometer reading is >10 mm (0.4  in. )  H20,
             the wet test meter is defective.   If  the  wet test
             meter is defective, and if the defects(s) (e.g., bad
             connections   or  joints)  cannot   be   found   and
             corrected, return it to the manufacturer for repair.

    6.  Continue  the  operation until the 1-gal container is al-
most full.  Plug the inlet to the saturator.  If no  leak exists,
the  flow of liquid to the gallon container should stop.  If  the
flow continues, correct for leaks.  Turn the siphon system off by
closing the valve, and unplug the inlet to the wet test meter.

    7.  Read  the  initial  volume  (V.*)  from the v;et test meter
dial, and record  on  the  wet test meter calibration log. Figure
2.2.

    8.  Place a clean, dry volumetric  flask  (Class-A) under the
siphon  tube, open the pinch clamp, and fill the volumetric flask
to the mark.  The volumetric flask must be large enough  to allow
at least one complete revolution of  the  wet test meter with not
more than two fillings of the volumetric flask.

    9.  Start  the flow of water, and record the maximum wet test
meter manometer reading  during the test after a constant flow of
liquid is obtained.

   10.  Carefully fill the volumetric flask,  and  shut  off  the
liquid flow at the 2-L mark.  Record the final  volume  shown  on
the wet test meter.

   11.  Steps 7 through 10 must be performed three times.

    Since  the  water  temperature in  the  wet  test  meter  and
reservoir has been  equilibrated  to  the ambient temperature and
the  pressure  in  the wet test meter will equilibrate  with  the
water reservoir  after the water flow is shut off, the air volume
can be compared directly with  the  liquid  displacement  volume.

-------
Wet test meter  serial number    45"
                        Date
Range of wet  test meter flow  rate 0~~12-0 I—I#ilt\


Volume of test flask VQ =   J2..00L-
                      3   •••^•a- I   ••••••••! II •

  Satisfactory leak check?
  Ambient temperature of  equilibrate liquid in wet test meter and reservoir    7*f- /"*
Test
number
1
2
3
Manometer
reading, a
mm t^O
r
5"
f
Final
volume (Vj ) ,
L
/.??
2.00
Z.OD
Initial
volume (V.),
L
0
0
0
•total
volume, (V )
L
/??
2.00
z.oo
Flask
volume (V ) ,
L
2.. 00
Z.6to
Z..CA
Percent
error, c
%
•o.r
d
0
aMust be  lesa than  10 mm  (0.4  in.)  H20.
Calculations:


      Vc - V,.
   .
  m
c% error = 100 (V_ - Va)/Vn =»
                 . d    S   o
                                  fi.f
              (+1%).
Signature of calibration person
                        Figure 2.2.   Wat toot motor calibration log.
 O
                     O
                                                                                                          *a a en
                                                                                                          W 0) (D
                                                                                                         IQ-ft O
                                                                                                          a> ro rt
                                                                                                              H-
                                                                                                          iN > O
                                                                                                            t) P
                                                                                                            h
                                                                                                            H-2
                                                                                                            H 0
                                                                                                            O> CO
                                                                           H1 O1
                                                                           VO •
                                                                           CO tO
                                                                           01
                                                                                                          O

-------
                                              Section No. 3.15.2
                                              Date April 16, 1986
                                              Page 5

Any  temperature  or  pressure  difference  would  be  less  than
measurement error and would not affect the final calculations.

    The error should not exceed +1%; if this  error  magnitude is
exceeded,  check all connections within the  test  apparatus  for
leaks, and  gravimetrically  check  the  volume  of  the standard
flask.  Repeat the calibration  procedure,  and  if the tolerance
level  is  not met, adjust the liquid level within the meter (see
the manufacturer's manual) until the specifications are met.

2.1.2  Sample Metering System - The sample metering  system, con-
sisting  of  the  drying tube, needle valve, pump, rotameter, and
dry  gas  meter,  is initially calibrated by stringent laboratory
methods before it is used in the  field.  The calibration is then
rechecked after each field  test  series.   This recheck requires
less  effort  than  the  initial  calibration.   When  a  recheck
indicates  that  the  calibration  factor has changed, the tester
must  again perform the complete laboratory procedure  to  obtain
the new calibration factor.  After the meter is recalibrated, the
metered  sample  volume  is multiplied by the calibration  factor
(initial  or  recalibrated) that yields the lower gas volume  for
each test run.

    Initial  Calibration - The metering system should be calibra-
ted  when  first  purchased  and  at  any time the posttest check
yields a calibration factor that does not agree within 5% of  the
pretest  calibration   factor.    A  calibrated  wet  test  meter
(properly sized, with +1% accuracy)  should  be used to calibrate
the metering system.

    The metering system should  be  calibrated  in  the following
manner before its initial use in the field.

    1.  Leak  check the  metering  system  (drying  tube,  needle
valve, pump, rotameter, and dry gas meter) as follows:

        a.   Temporarily  attach a suitable rotameter (e.g., 0-40
             cm /min) to the  outlet  of  the  dry gas meter, and
             place  a  vacuum  gauge  at  the inlet to the drying
             tube.

        b.   Plug  the  drying  tube  inlet.  Pull a vacuum of at
             least 250 mm (10 in.) Hg.

        c.   Note the flow rate as indicated by the rotameter.

        d.   A leak of <0.02 L/min must be recorded or leaks must
             be eliminated.

        e.   Carefully  release the vacuum gauge  before  turning
             off pump.

-------
                                              Section No. 3.15.2
                                              Date April 16, 1986
                                              Page 6
                      i
    2.  Assemble the apparatus,' as shown in Figure 2.3,  with the
wet test meter replacing the  drying tube and impingers; that is,
connect the outlet of the wet test meter to the inlet side of the
needle valve and  the  inlet side of the wet test meter to a sat-
urator  which  is  open  to  the  atmosphere.  Note; Do not use a
drying tube.

    3.  Run  the  pump  for  15 minutes with the flow rate set at
450 cc/min to allow  the  pump  to  warm  up  and  to  permit the
interior surface of the wet test meter to become wet.

    4.  Collect the information required  in  the forms provided,
Figure 2.4A  (English units) or 2.4B (metric units), using sample
volumes equivalent  to  at least five revolutions of the dry test
meter.  Three independent runs must be made.

    5.  Calculate Y. for each of the three  runs  using  Equation
2-1.  Record the values in the form (Figure 2.4A or 2.4B).
                                   460°F or 273°C)   Equation 2-1
              v,q p™ (t  + 460°F or 273°C)
where:         d  m,  w
                                                      o
   /      Dm \
Vw Vpm + 13'6/  <*d +	
                         ><•»

                                                        O
        Y. = ratio for each run of volumes measured by the wet
             test meter and dry gas meter, dimensionless
             calibration factor,

                                                 3    3
        V  = volume measured by wet test meter, m  (ft  ),
         Vr

        P  = barometric pressure at the meters, mm (in.) Hg,

        D  <= pressure drop across 4:he wet test meter, mm (in.)
             H20,

        t, = average temperature of dry gas meter, °C (°F),
                                                    3    3  '
        Vd = volume measured by the dry gas meter, m  (ft  ), and

        t  = temperature of wet test meter,  C (°F).
         W .   . ,

    6.  Adjust and recalibrate or reject the dry gas meter if one
or more  values of Y. fall outside the interval Y +0.02Y, where Y
is the average for triree runs.   Otherwise,  the  Y  (calibration
factor) is acceptable  and  is  to  be used for future  checks and
subsequent test runs.   The completed form should be forwarded to     ^_^^
the  supervisor  for approval, and then filed in the  calibration     f)
log book.                                                             \*^/

-------
THERMOMETER
                                                                   MANOMETER
                                                                                 AIR INLET
              Figure 2.3.   Sample metering system calibration  setup.
V D W
0) 0) (0
IQ rt O
(D (P rt
    H-
-J > O
  T3 3
  n
  H- 21
  H O
                                                                                                    CO
                                                                                                   M cn
                                                                                                   vo •
                                                                                                   oo to
                                                                                                   cn

-------
Date
 2/2-
                   Calibrated by
                                                     Meter box number   ££~\    Wet  test  meter number  /<3/-/4
Barometer pressure, P,
                     m
                                      in. Hg   Dry gas meter temperature correction  factor
Wet test
meter
pressure
drop
.a
in. H20
o.tt
6.2.?
0.1$
Rota-
meter
setting
(R8>.
ft3/nin
0.0 Ik
0.011*
6. OH,
Wet test
meter gas
volume
72,
730.02!
733. /SB
Wet test
meter
gas temp
(tw>>
°F
72-
72-
72-
Inlet
gas
temp
'V*
op
80
82.
84
Dry test meter
Outlet
gas temp
(
ez-
Tirae
of run
(9),d
min
66
 O
                                                                                                               TJ 3
                                                                                                                h
                                                                                                                H- 2
                                                                                                                H O
                                                                                                                  •
                                                                                                                H
                                                                                                                CT> CO
                                     .  -3)
                                                     and
                                                                                                                  O1
                                                                                                                CD
                Figure 2.4A.  Dry gas meter calibration data form  (English units).
O
                                                         O
                                                                                                            O

-------
Date  2
                    Calibrated by
X>
                                       »
                                                     Meter box number   E:£~l    Wet  test  meter number  /Of "
Barometer pressure, Pm *    748
                                                 Dry gas meter temperature correction  factor  /v4     °C
Wet test
meter
pressure
drop
•
°C
2*-
Z8
2-f
Dry test meter
Outlet
gas temp
t>
66
b&
Average
ratio
(Y^,6
/.0&
/,v/6
l,oz
                                                                                                               H tn
                                                                                                               vo t
                                                                                                               oo to
                                                                                                               cn
                   Figure 2.4B.  Dry gas meter calibration data form  (metric units).

-------
o
                                              Section No.  3.15.2
                                              Date April 16,  1986
                                              Page 10

    Posttest Calibration Check - After each  field  test  series,
conduct a calibration  check  as  in  Subsection  2.1.2  with the
following exceptions:

    1.  The leak check is not conducted  because  a leak may have
been corrected that was present during testing.

    2.  Three  or  more revolutions of the dry gas meter  may  be
used.

    3.  Only two independent runs need be made.

    4.  If a temperature-compensating dry gas meter was used, the
calibration temperature for the dry gas meter must be  within 6°C
(10.8 F) of the  average  meter  temperature  observed during the
field test series.

    When a lower meter calibration factor is obtained as a result
of an  uncorrected  leak,  the tester should correct the leak and
then determine the calibration  factor  for  the leakless system.
If the new calibration  factor  changes  the compliance status of
the facility  in  comparison  to the lower factor, either include
this information  in the report or consult with the Administrator
for reporting  procedures.   If  the  calibration factor does not
deviate by >5% from the initial calibration  factor Y (determined
in  Subsection  2.1.2), then the dry gas meter  volumes  obtained
during the test series are acceptable.  If the calibration factor
does deviate  by  >5%,  recalibrate  the  metering  system  as in
Subsection  2.1.2;  for  the  calculations,  use  the t:alibration
factor  (initial  or recalibration) that  yields  the  lower  gas
volume for each test run.

2.2  Thermometer

    The thermometer(s) on the dry gas meter inlet used to measure
the  metered sample gas temperature should be initially  compared
with a mercury-in-glass  thermometer  that meets ASTM E-l No. 63C
or 63F specifications:
                                                            *
   1. Place  the  dial  type or an equivalent, thermometer- and the
mercury-in-glass thermometer  in  a  hot water bath, 40 C to 50 C
(104  to 122 F).  Compare the readings after the bath stabilizes.

   2.  Allow  both  thermometers  to  come  to  room tenperature.
Compare the readings after the thermometers stabilize.

   3.  The dial type or equivalent  thermometer  is acceptable if
(1) values agree within 3 C (5.4 F) at both points (steps I and 2
above) or (2) if the temperature differentials at both points are  /~~\
within 3 C (5.4 F)  and  the temperature differential is taped to  I   J
the  thermometer  and  recorded  on  the  meter  calibration form  ^-^
(Figure 2.4A or 2.4B).
O

-------
                                              Section No. 3.15.2
                                              Date April 16,  1986
                                              Page 11

    4.  Prior to each field trip, compare the temperature reading
of the mercury-in-glass thermometer at room temperature with that
of the thermometer  that  is part of the metering system.  If the
values  or  the  corrected  values are not within 6 C (10.8°F) of
each other, replace or recalibrate the meter thermometer.

2.3  Rotameter

    Method 7D recommends (optional) that the tester calibrate the
rotameter prior to  each  test.   Before being sent to the field,
the rotameter should be  cleaned  and maintained according to the
manufacturer's  instructions.  For this reason, it is recommended
(optional) that the calibration curve and/or  rotameter  markings
be  checked  upon  receipt  and  then routinely checked with  the
posttest metering system check.  The rotameter may  be calibrated
as follows:

    1.  Ensure  that  the rotameter has been cleaned as specified
by the manufacturer and is not damaged.

    2.  Use the manufacturer's  calibration curve and/or markings
on  the  rotameter  for the initial calibration.   Calibrate  the
rotameter  as  described  in  the metering system calibration  of
Subsection 2.1.2,  and  record  the  data on the calibration form
(Figure 2.4A or 2.4B).

    3.  Use the rotameter for testing  if  the pretest calculated
calibration is within 450 +25 cc/min.   If, however, the calibra-
tion point is not within 5%~, determine a new  flow  rate setting,
and   recalibrate   the  system  until  the  proper  setting   is
determined.

    4.  Check  the  rotameter   calibration  with  each  posttest
metering system check.  If the rotameter check is  within  10% of
the  450 cc/min  setting,  the  rotameter   is  acceptable.   If,
however,  the  check  is not within  10%  of  the  flow  setting,
disassemble  and  clean  the  rotameter,   and   perform  a  full
recalibration.

2.4  Barometer

    The field barometer should be adjusted initially  and  before
each  test  series  to  agree  within  2.5 nun (0.1 in.) Hg with a
mercury-in-glass barometer  or  with  the pressure value reported
from a nearby National Weather Service Station  and corrected for
elevation.  The tester should be aware that the pressure readings
are  normally  corrected to sea level.  The uncorrected  readings
should be obtained.  The correction for the elevation  difference
between the weather station  and  the  sampling  point  should be
applied  at  a  rate  of  -2.5  mm  Hg/30  m (-0.1 in. Hg/100 ft)
elevation increase, or vice versa for elevation decrease.

-------
                                              Section No. 3.15.2
                                              Date April 16, 1986
                                              Page 12

    The calibration checks  should  be  recorded  on  the pretest
sampling form (Figure 2.5).

2.5  Analytical Balance

    The analytical balance  used  to  weigh  the reagents for the
nitrate  stock  standard  should  be  calibrated by the following
procedure:

    1.  Zero the balance.

    2.  Place a 5-g Class-S weight  on  the  balance.  Record the
    balance reading for the 5-g weight.

    3.  Place a 10-g  Class-S  weight on the balance.  Record the
    balance reading for the 10-g weight.

    4. The balance readings for the 5-g and 10-g weights must  be
    within 2 mg of the actual weights.

    5.  If the balance readings are greater  than +2 mg either of
    the actual weights, repair the balance or contact the balance
    manufacturer.

2.6  Ion Chromatograph System

2.6.1   Performance Check of the Ion Chromatograph  -  Method  7D
states  that  the  instrument_ used  for  analysis should provide
adequate  resolution  of  N0~   and should be able to resolve and
detect nitrite ion (N02~).  It is recommended that the instrument
be  performance checkea prior to initial use to ensure  that  the
instrument can meet the above criteria.                      --,-..*

    Method  7D  does  not  quantify the criteria  for  acceptable
instrument  performance.   The  numerical  limits  and procedures
given below are offered from a purely technical viewpoint.  Their
observance should ensure  that  the  instrument conforms with the
method,  but  should not be interpreted as  a  requirement.   The
preliminary considerations follow.                          .     ,

    Conductivity Detector  -  Prior  to its initial use, the con-
ductivity detector of the ion Chromatograph  should be calibrated
by the method described  in  the  operator's  manual.  After this
initial  calibration, a quality control sample should be analyzed
to check the detector response.   A quality control sample should
be analyzed immediately after the  initial  calibration curve for
each analytical run and the concentration compared  to the values
obtained for the same  QC  sample  in  the  past.  If the control
limits  are  exceeded,  the  analysis  must  be stopped until the
problem is found.

    Integrator - Many ion chromatographs  are equipped with elec-
o
 o
 o

-------
                                              Section  No.  3.15.2
                                              Date April  16,  1986
                                              Page 13
Date z'Z-^    - 	   Calibrated by             	
     ^   ,

Meter box number _£^—/


Dry Gas Meter*

Pretest calibration factor =  /.O&O (within 2% of average factor
  for each calibration run).

Rotameter

Pretest calibration factor (Y ) or setting =   /'.00     (between
  400 and 500 cc/min).

Dry Gas Meter Thermometer

Was a pretest temperature correction made? 	yes  A  no

If yes, temperature correction 	 (within 3°C (5.4°F) of
  reference values for calibration and within 6 C (10.8 F) of
  reference values for calibration check).

Barometer

Was the pretest field barometer reading correct?  X yes 	no
  (within 2.5 mm (0.1 in.) Hg of mercury-in-glass barometer).
*Most significant items/parameters to be checked.
              Figure 2.5.  Pretest sampling checks.

-------
                                              Section No.  3.15.2
                                              Date April 16,  1986
                                              Page 14

tronic  integrators  which,  if  properly used,  give  results  of
greater  accuracy and precision than manual techniques.    (Manual
techniques include quantification  based upon measuring: (a)  peak
height, (b) peak area by triangulation, (c) peak area  by  multi-
plying peak height  times the peak width at half-height, (d)  peak
area by cutting  out  the  peak and weighing it on a balance, and
(e) peak area by planimetry.)   However, an electronic integrator
is a potential source of error  if integration parameters are not
set up correctly.   For  example,  when the Hewlett Packard 3390A
Recording Integrator is used in the peak area mode, the processes
of recognizing and  integrating  peaks  in the data signal depend
upon  the  values  chosen  for  PK  WD  and THRSH.  If these  two
parameters are mismatched to each other  or  to  the data signal,
peaks will be missed by the integrator.  The appropriate sections
of  the  operator's  manual  should   be  read  carefully  before
selecting and setting integrator parameters.

    Electronic integrators,  used  in  the peak height mode,  have
been demonstrated to give  equally  good results as the peak area
mode, and therefore, many laboratories have  chosen  to  use this
simpler method.

    The  performance of the integrator in either mode  should  be
checked using a quality  control  sample  as  described above.  A
second check of the integrator's  performance can be made by com-
paring its results to those obtained manually.  If the integrator
is functioning properly, results should agree within 5 percent.

    Sample Injection Device Contamination Check - The analyst  is
encouraged to check the sample injection device for contamination
by  injecting  water  before   the   calibration   standards  are
analyzed.  Contaminants  will  appear  as  peaks on the chromato-
gram.   Repeated  injections  of  water  should be used to remove
contaminants from the sample injection device.   If certain peaks
remain  after several injections, then  the  water  may  be  con-
taminated and should be replaced.

    Separation  of  Nitrate,  NO,," - To ensure  accurate  results
from the ion chromatographic analysis, baseline separation of the
NOg  peak from the other ion peaks should be achieved.  A  source
of SO." in a sample may be sulfur dioxide present in the effluent
stream sample.  Figures 2.6a and 2.6b show two chromatograms, one
having overlapping N0«  and S04~  peaks,_ and  the  other  having
baseline separation or the  N0o~ and SO4~ peaks.

    The analyst is encouraged to check the performance of the ion
chromatograph system before analyzing samples  in order to ensure
that baseline separation of N03~ is attainable.
o
o
    The  ion  chromatograph can be performance  checked  using  a   /~*.
solution  containing NOg~ and_SO4~ for compliance purposes  or  a   (   ]
solution containing NO0 , NO0~,  and  S0.~  if  the nitrate is to   V—/

-------
                                          Ssction No. 3.15.2
                                          Date April 16, 1986
                                          Page 15
Figure 2.6a.  Example chromatogram having overlapping peaks.
Figure 2.6b.  Example chromatogram showing baseline
              separation of peaks.
                                                      "1

-------
                                              Section No.  3.15.2
                                              Date Ap
                                              Page 16
Date April 16,  1986 {J
be quantified.  A solution that' will provide  rigorous conditions
involves the use of KN03  working standard solution (described io
Section  3.15.5,  page  3)  and  N02   (if  applicable) and  SO.
solutions, the preparation of which are addressed below.

    The SO," solution is prepared as  follows: Weigh out 0.231 of
sodium sulfate (Na2SO.), and  transfer  it to a beaker.  Dissolve
the Na2S04 in water, quantitatively  transfer  the  solution to a
2 50-ml volumetric flask,  and  finally,  dilute  to the mark with
water.

    The concentration of the solution is 625  yg  S04~/ml.  Sodium
sulfate (Na^SO.) is  a  component  of  the pusher solution in the
Orsat  apparatus used for Method 3.  It is not  special  and  has
been  chosen  because of its probable availability.   Other  SO.
reagents can be used.

    If the nitrite is to be  quantified,  then  separation_of the
nitrate  peak  should  also be checked. To prepare the N02~ stock
solution, first weigh  out  52.5  mg  sodium  nitrite  (NaNOO and
transfer   it   to  a  beaker.   Dissolve  the  NaN02  in  water,
quantitatively transfer  it  to  a  250-ml  volumetric flask, and
finally,  dilute to the mark with water.   To  prepare  the  N02
working  solution,  pipet  10.0  ml  of the stock solution into a
100-ml volumetric  flask,  and  dilute to volume with water.  The
concentration of the working solution is 14 y g NO«~/ml.

    To prepare the performance check solution, pipet 1O ml of the
KNOg working standard solution,  8 ml of the SO." solution, and 1
ml  of the N0~  working solution ( if applicable;  into  a  200-ml
volumetric flask, and dilute to the mark with water.

    The concentration of N03~ in the  performance check sample is
7.5  yg  NO,, /ml,  which  corresponds  to  a NO  level around the
emission standard  for  coal-fired boilers subject to 40 CFR Part
60, Subparts D or Da.  This correspondence  also  is based on the
assumptions that sampling is conducted for one hour at 500 ml/min
and that the effluent sample is 12% (v/v) CO2.

    The SQ4~ concentration of the  performance  check  sample  is
25 yg S04~/ml, which corresponds to an SO2 level of roughly  1000
ppm (for a one-hour  sample acquired at 500 ml/min and containing
12% (v/v)  c°2^*   This  concentration  level should be more than
adequate for situations involving the application of Method 7D to
sources subject to  40  CFR  Part  60,  Subpart_ D;  thus,  it is
recommended  that  analysts  decrease  the  SO." concentration in
proportion  to  the  S0?  levels expected for the effluent.   For
example, if the effluent concentration of SO,,  were 500 ppm, 5 ml
(rather  than  10  ml)  of  the  S04   solution would be used  in
                    o

-------
                                              Section No. 3.15.2
                                              Date April 16, 1986
                                              Page 17

preparing   the   performance  check  sample.   For  applications
upstream of flue gas desulfurization  systems  at sources subject
to 40 CFR Part 60, Subpart Da,  the opposite situation may exist,
and it is recommended that the concentration of SO." be increased
accordingly.

    The  NO?-  concentration of the performance check solution is
0.07  yg NO2~/ml.  This corresponds to 6 ppm NO2 for  a  one-hour
sample acquired at 500 ml/min and containg 12% fv/v) CO2«

    The performance check solution should be  analyzed  with  the
calibration  standards  during  the  initial  check  of  the  ion
chromatograph's calibrations.   The  same experimental conditions
should  be observed for the solution and the  standards.   Figure
2.7_provides _an  example chromatogram that shows where the N02~,
NO
and SO.  can be expected to elute.
2.6.2  Preparation of Calibration Curve - Method 7D gives general
instructions  for  preparing  the calibration curve for  the  ion
chromatograph.  Accordingly, the method requires that:

    (a)  at least four calibration standards be prepared?

    (b)  the  concentration  range of the  calibration  standards
         cover  the  concentration  range  of  the  samples being
         analyzed;

    (c)  the calibration standards  be  prepared  from  the  KN03
         standard solution using pipettes having  volumes  1.0 nl
         or greater;

    (d)  the calibration standards be analyzed and the results be
         interpreted in the same manner as for  the samples being
         analyzed;

    (e)  the results of the analyses of the calibration standards
         (in units  of either peak height or peak area) should be
         plotted versus the standards'  concentrations  (in units
         of vg N00 /ml);
                 o                                          •
    (f)  the plotted points define a linear relation;

    (g)  the calibration equation be determined  from  the points
         using linear regression; and

    (h)  the calibration standards  be analyzed twice in order to
         compensate for  any  drift  in  the  response of the ion
         chromatograph.

    The method leaves to the analyst details including:

-------
                                           Section No.  3.15.2
                                           Date April  16, 1986
                                           Page 18
                                                  o
                     SO.    5.5  minutes
                     NO,    3.7  minutes
                                                 1.4 minutes
                                                                O
Figure 2.7.
Chromatogram showing resolution of nitrite,
nitrate, and sulfate peaks.
o
                                                      I A'

-------
    (a)


    (b)


    (c)
the concentration
standards;
                  Section No. 3.15.2
                  Date April 16, 1986
                  Page 19

values for the individual calibration
the  degree of linearity of the calibration  curve
will ensure quality results; and
                                 that
the procedure to be used to compensate  results
ion chromatograph's drift.
                              for the
    Concentration values for calibration standards -  The step-by
step-procedures  for  preparing  the  calibration  standards  and
preparing the calibration curve are given in Section 3.15.5.

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                                                           Section No.  3.15-2
                                                           Date April 16,  1<>S6
                                                           Page 20
                                                                  o
            Table 2.1.  ACTIVITIY MATRIX FOR CALIBRATION OF EQUIPMENT
Apparatus
 Acceptance Limits
Frequency and method
    of measurement
Action if
requirements
are not net
Wet test meter
Capacity of at least 2
L/min and an accuracy
within 1.0#
Calibrate initially and
then yearly by liquid
displacement
Adjust until
speci fi cations
are met, or re-
turn to nanu-
facturer
Dry gas meter
Y. = Y+0.02Y at a
flow rate of about
450 cc/min
Calibrate vs. wet test
meter initially and
when the posttest check
is not within Y+0.05
Repair end then
recalibrate, or
replace
Dry gas meter
 thermometer
Within 3C (5.
of true value
Calibrate each initially
as a separate component
against a mercury-in-
glass thermometer; after
train is assembled
before each field test,
compare with mercury-in-
glass thermometer
Adjust, deter-  /~-^
nine a constant f    ]
correction
or reject
Rotameter
Clean and maintain ac-
cording to manufactur-
er's instructions (re-
quired) ; calibrate to
+5X (recommended)
Initially and after each
field trip
Adjust and recal-
ibrate, or reject
Barometer
Within 2.5 mm
(0.1 in.) Hg of
mercury-in-glass bar-
ometer or of weather
station value
Calibrate initially
using a mercury-in-glass
barometer; check before
and after each field
test
Adjust  to agree
with certified
barometer
Analytical
  balance
Weight within 2 mg of
standard weights
(Class-S)
Use standard weight be-
fore preparation of
working solution
Repair or return.
to manufacturer
(continued)
                                                                  O

-------
                                                           Section No.  3.15.2
                                                           Date April 16,  1986
                                                           Page 21
Table 2.1.   (continued)
Apparatus
Acceptance Limits
Frequency and method
    of measurement
Action if
requirements
are not cet
Ion chromato-
  graph
Calibrate prior to each
set of sample analyses
With each set of field
samples; calibration
standards prepared from
potassium nitrate
Interpret data
using another
technique; e.g..
if using peak
height, change
to peak area;
analyze addition-
al calibration
standards; cali-
brate conductiv-
ity detector;
consult oper-
ator's nanual

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o
o
o

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                                              Section No. 3.15.3
                                              Date April 16,  1986
                                              Page 1
3.0  PRESAMPLING OPERATIONS
    The quality assurance activities for presampling  preparation
are summarized in Table  3.1  at  the  end  of this section.  See
Section 3.0 of this  Handbook  for  details  on  preliminary site
visits.

3.1  Apparatus Check and Calibration

    Figure 3.1 or a similar form is recommended to aid the tester
in preparing an  equipment  checklist,  status  report  form, and
packing list.

3.1.1  Sampling Train - The  schematic for the NO  sampling train
is given  in  Figure  1.2.   Commercial models ofxthis system are
available.   Each  individual  or  fabricated train  must  be  in
compliance with the specifications in Method 7D, Section 3.15.10.

3.1.2  Probe - The probe should be cleaned internally by brushing
first  with tap water, then with deionized distilled  water,  and
finally  with acetone.  Allow the probe to dry in  the  air.   In
extreme cases, the glass or stainless steel  liner can be cleaned
with stronger  reagents; the objective is to leave the liner free
from contaminants.  The probe's heating system  should be checked
to see whether  it is operating properly.  The probe must be leak
free when sealed at the inlet or tip and checked  for  leaks at a
vacuum  of  250  nun  (10 in.) Hg with the meter box.   Any  leaks
should be corrected.  The liner should be sealed inside the metal
sheath to prevent diluent air from entering the source since most
stacks are under negative pressure.

3.1.3  Restricted Orifice  Impingers  and  Glass Connectors - All
glassware should  5i  cleaned  with  detergent and tap water, and
then with  reagent  water.   Any  items that do not pass a visual
inspection for cracks or breakage must be repaired or discarded.

3.1.4  Drying Tubes - Drying  tubes  should  be packed with 6- to
16-mesh silica gel and sealed at both ends.

3.1.5  Valve and Rotameter - Prior to each field trip  or  a^b any
sign of erratic  behavior,  the  flow control valve and rotameter
should be cleaned according to the maintenance  procedure  recom-
mended by the manufacturer.

3.1.6  Pump- - The vacuum pump  and  oiler  should  be serviced as
recommended by  the  manufacturer,  every 3 months, or every 10th
test   (whichever  comes  first),  or   upon   erratic   behavior
(nonuniform or insufficient pumping action).

3.1.7   Dry Gas Meter - A dry gas meter calibration check  should
be  made  in accordance with the procedure in Section 3.15.2.  An
acceptable posttest check from the previous test is sufficient.

-------
                                              Section No.  3.15.3
                                              Date April  16,  1986
                                              Page 2
o
Apparatus check
Probe
Type liner/
Glass X
Stainless
steel
Other 	
Heated properly*
Leak checked
Filter
Glass wool
Other

Glassware
Restriced
orifice
impinger
Size
Type

Meter System
Leak-free pumps*
Rate meter*
Dry gas meter*
CO2 Measurement
Orsat iS
Fyrite

Reagents
Water
Potassium
permanganate*
Silica gel
Other
Barometer
Drying tube
Acceptable
Yes
/
•"
,/"
tX
iX
iX
iX
tx
X"
iX
I/"
,/
/
iX
NO







Quantity
required
f
c5Al^// k>/
/f
Z
1
I
Z.
z ^/
z «*/
$-#
1
b
Ready
Yes
X
*x
iX
t/
iX
•X
^
^
ix-
*s
^
\^
No







Loaded
and packed
Yes
*x
^x
«x
^
l^
l^
i/
ix- .
(X
u^
NO







                                                                   O
* Most significant items/parameters to be checked.
                Figure 3.1.  Pretest preparations.
                                                                    O

-------
                                              Sectibn No. 3.15.3
                                              Date April 16, 1986
                                              Page 3

 3.1.8   Thermometers -  The  thermometers  should be compared with
 the  mercury-in-glass  thermometer  at room temperature prior  to
 each field trip.

 3.1.9   Barometer  -  The  field barometer should be compared with
 the mercury-in-glass barometer or with a National Weather Service
 Station reading prior to each field trip.

 3.1.10  COp Analysis - Method  3 sampling apparatus should be leak
 checked, and the reagents should  be  checked to ensure freshness
 (see Section 3.2 of this Handbook).

 3.2  Reagents for Sampling

    The following reagents are  needed  during the sampling phase
 of Method 7D:

 3.2.1   Water - Deionized distilled  water  should conform to ASTM
 specification  D1193-82,  Type  III   (see  Subsection  1.4.1  for
 detailed specifications).

 3.2.2    Potassium   Permanganate/Sodium  Hydroxide  (KMnO./NaOH)
 Solution - Dissolve 40.0 g  of KMNO4  and 20.0 g of NaOH in 940 ml
 of water.

 3.3  Packaging Equipment for Shipment

    Equipment should be packed in rigid containers  to protect it
 against rough handling during shipping and field operations.

 3.3.1 Probe - The inlet and outlet  of  the  probe must be sealed
 and protected from breakage.  A suggested container  is  a wooden
 case  lined  with  polyethylene  foam or other suitable  packing
 material; the case  should  have separate compartments for indiv-
 idual devices.   The  case should be  equipped with handles or eye
 hooks that can withstand hoisting, and should be rigid to prevent
 bending or twisting during shipping and handling.

 3.3.2 Impingers,   Connectors,  and Assorted Glassware - All ijnpin-
 gers  and  glassware  should be packed in a rigid  container  and
protected by polyethylene foam  or  other suitable packing mater-
 ial.  Individual  compartments for glassware help to organize  and
protect  each  item.   The  impinger  train  may  be charged  and
 assembled in the  laboratory if sampling is to be performed within
 24 hours.

3.3.3 Drying Tubes and Volumetric  Glassware  - A rigid container
 lined with polyethylene foam material protects  drying  tubes and
 assorted volumetric glassware.

3.3.4  Meter  Box  - The meter box,  which  contains  the  valve,
rotameter,  vacuum pump,  dry gas meter, and thermometer(s),  should

-------
be  packed  in
strong  enough
pump oil should be
is  advisable  to
failure.
                              Section No. 3.15.3
                              Date April 16, 1986
                              Page 4

a  rigid shipping container unless its housing is
to  protect components during travel.  Additional
   packed if oil  is  required for operation.  It
   ship  a  spare  meter box in case of equipment
                                                                   o
3.3.5 Wash Bottles and Storage Containers  -  Storage  containers
and  miscellaneous  glassware  should  be  packed   in   a  rigid
foam-lined   container.    Samples  being  transported   in   the
containers   should  be  protected  from  extremely  low  ambient
temperatures (below freezing).
                                                                   O
                                                                   o

-------
                                                               Section No. 3-15.3
                                                               Date April 16. 1986
                                                               Page 5
               Table 3.1.  ACTIVITY MATRIX  FOR PRESAMPLING OPERATIONS
Operation
Probe
 Acceptance limits
1. Probe liner free
of contaminants
                  2. Probe leak free at
                  250 mm (10 in.)  Hg

                  3. No moisture conden-
                  sation
Frequency and method
    of measurement
1. Clean probe inter-
nally by brushing with
tap water, then deion-
ized distilled water,
then acetone; allow to
dry in air before test

2. Visually check for
cracks before test

3. Check out heating
system initially and
when moisture appears
during testing
Action if
requirements
are not met
1.  Retrace
cleaning pro-
cedure and
assembly
                                                  2.   Replace
                                                  3.   Repair
                                                  or replace
Restricted
 orifice impin-
 gers and glass
 connectors
Clean and free of
breaks, cracks, etc.
Clean with detergent,
tap water, and then
with deionized dis-
tilled water
Repair or
discard
Flow control
 valve and
 rotameter
Clean and without sign
of erratic behavior
(ball not moving)
Clean prior to each
field trip or upon
erratic behavior
Repair or
return to
manufacturer
Vacuum pump
Maintain sampling rate
of 400 to 500 cc/min
at a vacuum up to
250 mm (10 in.) Hg
Service every 3 DO. or
upon erratic behavior;
check oiler jars every
10th test
As above
Dry gas meter
Clean and within 2%
of calibration factor
Calibrate according
to Section 3.15.2;
check for excess oil
if oiler is used
As above
CO- analyzer
Leak-free and fresh
reagents
Leak check, and check
reagents
As above
(continued)

-------
                                                              Section No.  3-15-3
                                                              Date  April 16, 1986
                                                              Page  6
                                                               o
Table 3-1  (continued)
Operation
 Acceptance limits
 Frequency and method
     of measurement
Action if
requirements
are not met
Reagents

Sampling
Requires all ACS grade
reagents
Prepare and store in
sealed containers
Prepare new
reagent
Sample recovery
Requires water on
site
Quantity sufficient to re-
cover sample after testing
and clean impingers prior
to testing
Prepare new
reagent
Package Equip-
ment for Ship-
ment

Probe
Protect with poly-
ethylene foam
Prior to each shipment
Repack
O
Impingers,
 connectors,
 and assorted
 glassware
Pack in rigid con-
tainers with poly-
ethylene foam
As above
As above
Drying tubes,
 volumetric
 glassware
Sturdy container
lined with foam
As above
As above
Meter box
Meter box case and/or
container to protect
components, pack spare
meter box and oil
As above
As above
Wash bottles
 and storage
 containers
Pack in rigid foam-
lined container
As above
As  above
Samples
Protect from extreme
cold (below freezing)
As above
As  above
                                                                                 O

-------
                                              Section No. 3.15.4
                                              Date April 16, 1986
                                              Page 1
4.0  ON-SITE MEASUREMENTS
    On-site activities include  transporting the equipment to the
test  site,  unpacking  and  assembling,   sampling  for  nitrogen
oxides, and recording the data.  The quality assurance activities
are summarized in Table 4.1 at the end of this section.

4.1  Transport of Equipment to the Sampling Site

    The most efficient means of transporting the  equipment  from
ground level  to  the  sampling  site  (often above ground level)
should be decided during the preliminary  site  visit or by prior
correspondence.  Care should  be  taken  to prevent damage to the
equipment or injury to  test  personnel  during  the  moving.   A
laboratory area should be designated  for preparing the absorbing
reagents, charging the impingers,  and sample recovery,

4.2  Preliminary Measurements and Setup

    Method 7D outlines the procedure  for determining the concen-
tration  of  nitrogen  oxides in the gas stream.  The accuracy of
the equipment that has been transported to the sampling  site and
that may have been handled roughly can be determined by  making a
one-point  check  of the rotameter reading against  the  dry  gas
meter reading at the test site.  Use Equation 3 in Figure 2.4A or
2.4B, and substitute dry gas meter readings in place  of wet test
meter readings (i.e., V.  =  V ).    Y .  should bebetween 0.9 and
1.1;  if  not,  the  me"er  box  has  lost  its  rate  or  volume
calibration.  The tester can  still  use  the  meter box, but the
data should not be released for. decision making until a post-test
recalibration  has  been  made.  If the dry gas meter calibration
factor  did  change,  the  dry gas meter volumes may have  to  be
corrected.  Record the test identification number on the sampling
data form, Figure 4.1.

4.3  Sampling

    The on-site sampling includes the following steps:

    1. Preparation  and/or  addition of the absorbing reagents to
the impingers.

    2.  Setup of the sampling train.

    3.  Connection to the electrical service.

    4.  Preparation  of  the probe (leak check of entire sampling
train and addition of particulate filter).

    5.  Check of rotameter setting.

    6.  Insertion of the probe into the stack.

-------
Plant name
Location
Operator
             Actvd
                   Ab.  3
City
Date
                                                            Section No. 3-15-4
                                                            Date April 16, 1986
                                                            Page 2
                                                                 M~T~
                                                                                  O
                                           Sample no.      AP — I
Probe length/material
Meter box no.
                                            Probe  setting
                                           Meter factor  (Y)
                                                                   * f~~
Sampling point location(s)
Rotameter setting
Initial leak check?
                    0.004-
                              fa im>nj /i'J'A Bar press mm  (in.) Hg
                                           Rotameter check?  4-& cc-mf/i
C0_ concentration  (1)
                                 (2)
      leak check? 0.OO&
   (3)  fa?-
                                                             avg
Sampling
time,
min
0
5~
/o
/S~
20
z£
50
35"
40
45"
5~0
5£T
60


Total
Clock
time
24 h
It '00
1(0$
II 10
II 75"
//20
//2£~
//30
y/3$~
II to
//45"
7/50
//sr
/200



Dry gas
meter
readings
L (ft3)
/40. Z-/S"
/42. 46. /
/44. 101
!4-(p. ^5"B
/ 4^.202-
/S7.4?f
/5"3.6?^
/5S". ^3
/5B.222
/60.480
/62.72^
764.^82
7(^7. 226


Total
27.0((
Sample flow
rate setting,
cc/min (ft^/min)
	
•4-52?
451?
452)
45"0
457)
4^0
4-£d
4^0
4£0
4-Sb
4-57)
4 SO



Sample volume
metered,_(V )
L (ft3) m
	
2.2-40
2.240
2. 2-5*7
2.244
2.262
2.245
Z.2S4
Z.Z6>^
2,256
2.248
2.25-4
2.244


Q •* ^ o ^^ • /
avg t-'t-^ I
Percent
deviation,3
*
	
-0,ZZ.
-0.4*7
+ 0,21
-0,31
+ 0.04
-0.21
J-0,15
t-0,80
f6,S/
-^)./3
+ OJ3
-0.31


Avg
dev ^«T^-
Dry gas
meter temp,
°C (°F)
	
72
74
7f /
75"" ^
76
76
76
7B
76
1^
76
7^?
*

Avg
76,4
Percent deviation =   m  ~   m avg x 100   (must be  less  than 10 percent).
                         V  avg

                   Figure 4.1.  Field sampling data form for NO .
                                                              X
                                                                                    O

-------
                                           •••'•'• Section No. 3.15.4
                                              Date April 16, 1986
                                              Page 3

     7.   Sealing of the  port.

     8.   Check  of the  temperature of the probe.

     9.   Sampling.

    10.   Measuring the CO2  concentration.

    11.   Recording of  the data in Figure 4.1.

A  final  leak check of the  train  is  always performed after samp-
ling.

4.3.1    Preparation  and/or Addition  of  Absorbing  Reagents  to
Collection System - Absorbing reagents  can  be prepared on site,
if necessary,  according to the directions in Subsection 1.4.1.

     1.   Use a  pipette or a graduated cylinder to introduce 200 ml
of alkaline permanganate   (KMnO./NaOH)  solution into each of the
three impingers.                            l

     2.   Place  in the  sampling train a drying tube that has new or
regenerated silica gel.

4.3.2    Assembling the Sampling Train  -  After  assembling  the
sampling train as shown in Figure 1.2, perform the following:

     1.   Adjust  probe  heater  to  operating  temperature.  Place
crushed  ice and water around the impingers.

     2.   Leak check the  sampling train  just  prior  to use at the
sampling  site  (not  mandatory)  by  temporarily  attaching   a
rotameter (capacity of  0  to 40 cc/min) to the outlet of the dry
gas  meter and  placing a vacuum gauge at or near the  probe inlet.
Plug the probe inlet, pull a vacuum of  at  least 250 mm (10 in.)
Hg,  and  note the  flow rate indicated by the rotameter. "A leakage
rate _< 2% of the  average   sampling  rate  is  acceptable.   Note:
Carefully release  the probe inlet  plug  before  turning  off the
pump.  It is suggested  (but not mandatory) that the pump be leak
checked  separately,  either prior to or after the sampling  run.
If prior to   the  run,  the pump leak check shall precede -the leak
check of the sampling train.  If after, the pump leak check shall
follow the train leak check.  To leak check the pump, proceed  as
follows.  Disconnect  the drying  tube  from  "the  probe  impinger
assembly.   Pull   a   vacuum of 250 mm (10 in.) Hg.  Plug or pinch
off  the  outlet  of  the  flow  meter, and then turn off the pump.
The  vacuum should  remain stable for at least 30 seconds.

     3.   Place a loosely packed filter of glass wool in the end of
the  probe,  and connect the probe to the first impinger.

4.3.3 Rotameter  Setting  Check  (Optional) - After leak checking
the  sampling train, disconnect the probe from the first impinger.

-------
o
                                              Section No. 3.15.4
                                              Date April 16,  1986
                                              Page 4

and  connect  the  filter  (optional).   The  filter  is  a  tube
containing approximately 20 g of 5-Angstrom  molecular  sieve  to
remove the NO  from  the ambient air.  Start the pump, and adjust
the flow to tne rotameter  setting to be used during the sampling
run.  After the flow has stablized, start  measuring  the  volume
sampled, as recorded by the dry gas meter and the sampling  time.
Collect sufficient volume  to  measure  accurately the flow rate,
and calculate the flow rate.  The average  flow rat© must be less
than 500 cc/min  for  the  sample  to  be valid; therefore, it is
recommended that  the flow rate be checked as above prior to each
run.  Record the sampling rate on the data form.

4.3.4 Sampling (Constant  Rate)  -  Sampling  is  performed  at a
constant rate  ofbetween 400 and 500 cc/min as indicated by the
rotameter during the entire sampling run.  The  procedure  is  as
follows:

    1.  Record  the  initial  dry  gas  meter readings, barometer
reading, and other data as indicated in Figure 4.1.  Double check
the dry gas meter reading.

    2.  Position  the  tip  of  the  probe at the sampling point,
connect  the  probe  to the first impinger, and start  the  pump.
Warning;   If  the  stack is under a negative pressure of >250 mm /~~~\
(10 in7)  H2O  while  disconnected  from the impinger, the  probe  (    )
should  be  positioned  at the sampling point,  the  sample  pump   —^
turned  on,  and  then  the probe immediately  connected  to  the
impinger to prevent  the  impinger  solutions from being siphoned
backwards.

    3.   Adjust the sample flow to the preselected flow rate (400
to 500 cc/min) as indicated by the rotameter.

    4.   Maintain  a  constant  rate within 10% during the entire
sampling run,  and  take readings .(dry gas meter, temperatures at
dry gas meter, and rate meter) at least ©very 5 minutes.

    5.   Refer to emission standards for  minimum  sampling  time
and/or  volume.  (For example, the Federal  standard  for  fpssil
fuel-fired steam generators specifies a  minimum sampling time of
60 minutes;  for  relative  accuracy  tests, when the SO^ concen-
tration is greater than 1200 ppm,  the sampling time should be 30
minutes. )  A  quick  calculation  can  be  made  after  half  the
sampling time to guarantee that the sampling rate will not exceed
500 cc/min.

    6.  During sampling, measure the CO,, content of the stack gas
near the  sampling  point  using Method 3.  The single-point grab
sampling procedure is adequate,  provided  the  measurements  are
made  at  least throe times (near the start, midway,  and  before  /""N
theend of a run) and provided  the  average  CO2 concentration is f   j
computed.   An  Orsat  (which  is  highly  recommended) or Fyrite  ^—

-------
analyzer may be used for this  analysis.
recorded on the data form (Figure 4.1).
                      Section No.  3.15.4
                      Date April 16,  1986
                      Page 5

                   The  results should be
    7.   Turn off the pump at the conclusion of each run,  remove
the probe from the stack, and record the final  readings.   Warn-
ing: Again, if the stack is under negative  pressure,  disconnect
the probe first, and turn off the pump immediately thereafter.
    8.  Conduct a leak
(mandatory).
check,  as  described in Subsection 4.3.2
    9.  Calculate the sampling rate.  The sample volume (AV ) for
each point  should  be  within 10% of the average sampling volume
for all points, and the average sampling rate for the test should
be less  than  500  cc/min.  If the average sampling rate exceeds
500 cc/min, the sample collection efficiency may be affected.

4.4  Sample Recovery

    Method 7D requires  transfer of the impinger contents and the
connector washings  to  a  polyethylene  storage container.  This
transfer  should  be  done in the "laboratory"  area  to  prevent
contamination of the test sample.

    After  completing  the  final  leak  check,  disconnect   the
impingers, and transport them to the cleanup area.  Cap  off  the
impinger section with the use of polyethylene or equivalent  caps
before  transport  to the cleanup area.  Transfer the contents of
the  impingers  into  a  labeled,  leak-free  polyethylene sample
bottle.  Rinse the  three  impingers  a  couple  of times and the
connecting tubes once  with  3-  to 15-ml portions of water.  Add
these washings to the same sample  bottle,  and  mark  the  fluid
level  on the side.  Place about 1OO ml of the absorbing  reagent
(KMnO./NaOH) in a polyethylene bottle, and label it for  use as a
blank during sample analysis (once for each test).  An example of
a sample label is shown in Figure 4.2.
Plant Ac-nvt Potyts Pfert^-
Site /$o/ 6z.r No. 3 San
Date 3/A5V84 Run
Front rinse 1 1 Front filter
Back rinse 1 1 Back filter
Solution KMnO^ / PJ&OH
Volume: Initial (pOOtiU—
Cleanup by rfed L£>cit,r

City Co&( fzwdt MT"
tple type A/Oy
L number A-P~ 1
	 1 Front solution 1 	 1
1 Bank solution ^
Level marked ^ m
Final 6>4-2- tuL- ^
0)
K









              Figure 4.2.  Example of a sample label.

-------
                                              Section No.  3.15.4    S~\
                                              Date April 16,  1986
                                              Page 6

4.5  Sample Logistics (Data) and Packing Equipment

    The  sampling  and sample recovery  procedures  are  followed
until the required number of runs are completed.   Log all data on
the Sample Recovery and Integrity  Data Form,  Figure  4.3.  If the
impingers,  and  connectors are to be used in the next test,  they
should be rinsed with  water,  and  a  new  drying tube should be
inserted into the sampling trian.  At the completion of the test:

    1.   Check  all sample containers for proper labeling  (time,
date, location, number of test, and any  other pertinent documen-
tation). Be sure that a blank has been taken.

    2.  Record all  data  collected  during  the  field  test  in
duplicate  by  using carbon paper or by using data  forms  and  a
field laboratory notebook.  One set of data  should  be mailed to
the base laboratory, given  to  another  team member, or given to
the Agency.  Hand  carrying  the  other  set  (not mandatory) can
prevent a very costly and embarrassing mistake.

    3.   Examine all sample containers and sampling equipment for
damage, and pack them for shipment to the base laboratory,  being
careful  to label all shipping  containers  to  prevent  loss  of
samples or equipment.

    4.   Make  a  quick check of the sampling and sample recovery
procedures using the data form,  Figure 4.4.
o
                                                                    o

-------
                                               Section No.  3.15.4
                                               Date April  16, 1986
                                               Page 7
Plant
ro
Sampling location  £>t>f(£*' /(£,.
                        Field Data Checks
Sample recovery personnel
Person with direct responsibility for recovered samples
Sample
number
1
2
3
Blank
Sample
identification
number
W-l



Date
of
recovery
3//S~/64
/ '


Liquid
level
marked
ix^



Stored
in locked
container
^



Remarks
Signature of field sample trustee
                      Laboratory Data Checks
Lab person with direct responsibility for recovered samples
Date recovered samples received
Analyst 	
Sample
number
1
2
3
Blank
Sample
identi f icat ion
number
frf-l



Date
of
analysis
3//&/M



Liquid
level
marked
f^



Stored
in locked
container
^^


-
Remarks
Signature of lab sample trustee
         Figure 4.3.  Sample recovery and integ

-------
                                              Section No.  3.15.4
                                              Date April  16,  1986
                                              Page 8
Sampling
Impinger contents properly selected, measured,  and placed in
impingers?* 	\/_	

Impinger Contents/Parameters*

1st: 200 ml of KMnO4/NaOH 	.X	

2nd: 200 ml of KMnO4/NaOH 	

3rd: 200 ml of KMn04/NaOH 	
Drying tube: 6- to 16-mesh silica gel

Probe heat at proper level?* 	
Crushed ice around impingers?  S?0 '
                                  *
Pretest leak check at 250 m

Leakage rate? _ 0,00 4-
                                  7

Pretest leak check at 250 mm (10 in.) Hg?
Check of rotameter setting?     ^.ST c-c-/**-!*-	   C  J

Probe placed at proper sampling point? 	
Flow rate constant at approximately 450 cc/min?*

CC>  concentration measured?*
Posttest leak check at 250 mm (10 in.) Hg?*

Leakage rate? _ 0. OO (0  £-/
Sample Recovery

Contents of impingers placed in polyethylene bottles?

Fluid level marked?*
Sample containers sealed and identified?* 	^
* Most significant items/parameters to be checked.


                  Figure 4.4.  On-site measurements.                (   )


                                                     .•/£*'

-------
                                                              -Section No. 3."
                                                              Date April 16,
                                                              Page 9
            Table 4.1.  ACTIVITY MATRIX FOR ON-SITE MEASUREMENT CHECKS
Activity
   Acceptance limits
Frequency and isethod
    of measurement
•Action if
requirements
are not net
Preparing and/
or adding
absorbing
reagents
Add 200 ml of KMnOj./
NaOH to the impingers
Add 40.0 g of KMnOj. and
20.0 g of NaOH to 940 ol
of water
Reassemble col-
lection system
Assembling
the sampling
train
1.  Assemble to speci-
fications in Fig. 1.2
                2.  A leakage rate
                of <2% of the average
                sampling rate
1.  Before each sampling
run
                          2.  Leak check before
                          sampling (recoonended) by
                          attaching a rotameter to
                          dry gas meter outlet,
                          placing a vacuun gauge
                          at or near probe inlet,
                          and pulling a vacuum
                          of > 250 mm (10 in.) Hg
1. Reassenble
                            2. Correct the
                            leak
Sampling (con-
 stant rate)
1.  Within 10% of
constant rate
                2.  Minimum accepta-
                ble time is -60 min
                and sampling rate
                less than 500 cc/min

                3.  Less than 2% leak-
                age rate at 250 mm
                (10 in.) Hg
                4.  Determine CO,
                content
1.  Calculate % devia-
tion for each sample
using equation in
Fig. 4.1
                          2.  Make a quick calcu-
                          lation prior to comple-
                          tion and an exact calcu-
                          lation after cospletion

                          3-  Leak check after
                          sampling run (mandatory);
                          use same procedure
                          as above
 1.   Repeat the
 sampling, or
 obtain accep-
 tance froa a
 representative
 of  the
 Administrator

 2.   As above
                          4.
                          using Method 3
    Measure CQ~ content
                            3-  As above
     As above
(continued)

-------
                                                              Section No. 3.15-4
                                                              Date April 16, 1986
                                                              Page 10
                                                                                  o
Table
           (continued)
Activity
                  Acceptance limits
Frequency and method
   of measurement
Action if
requi rements
are not met
Sample logistics
  (data) and
  packing of
  equipment
                  1.  All data are re-
                  corded correctly
                  2.  All equipment ex-
                  amined for damage and
                  labeled for shipment
                  3.  All sample con-
                  tainers properly
                  labeled and packaged
1.  Visually check upon
completion of each run
and before packing
                                          2.   As above
                                          3.  Visually check upon
                                          completion of test
1.  Complete
 the data form
                          2.  Redo test
                          if damage
                          occurred during
                          testing

                          3.  Correct uhen
                          possible
                                                                                  O
                                                                                   o

-------
                                              Section No. 3.15.5
                                              Date April 16, 1986
                                              Page 1
5.0   POSTSAMPLING OPERATIONS
    The postsampling operations for Method 7D include an apparat-
us  check,  a  barometer  check,  sample  preparation, and sample
analysis by ion chromatography.  The procedures for the apparatus
check and the barometer check are the same as in Method 6.  These
procedures are detailed in Section 3.5.5 in the Quality Assurance
Handbook for  Air  Pollution  Measurement Systems, Volume III and
are  not  discussed here.  The procedures for sample  preparation
and sample analysis  are  described  here.   Table 5.1 provides a
checklist summarizing the postsampling procedures.

5.1 Sample Preparation

    Sample  preparation  should not be started until the required
36-hour  conversion time  has elapsed for  complete, .conversion of
NO2~ to NO.-".  When using Method 7D for relative accuracy testing
of  continuous  emission  monitors,  the  sample can be  prepared
immediately if the nitrite in the sample is quantitated using the
procedures described in Section  5.2.   The  liquid  level in the
sample  container  should  be  checked to determine if sample has
been  lost  during   shipment.    If  a  loss  has  occured,  the
appropriate  steps  should be taken to correct for the loss.  The
sample is prepared  for  ion  chromatography by precipitating the
excess  permanganate  as manganese dioxide (MnO2).   A  5%  (v/v)
hydrogen  peroxide  (H2O2)  solution  is  used   to   reduce  the
permanganate to Mn02•   The MnO2 precipitate is removed by vacuum
filtration and the filtered  solution  is  volumetrically diluted
prior to chromatographic analysis.

5.1.1 Sample Loss Determination and Correction - Before preparing
the sample, it must be  allowed the full 36-hour conversion time.
Compare  the liquid level in the sample container to the mark  on
the  container.   If a noticeable amount of sample has been lost,
use the following procedure for correcting the sample volume:

   1.  Mark the new level of liquid on the sample container.

   2.  Transfer the sample to a 1-liter volumetric flask (V  . ),
and rinse the container with water.                        soj.n

   3.  Fill the sample container with water to the initial sample
level.  Transfer the water to a graduated cylinder, and determine
the original sample volume (vsoln )•

   4.  Fill  the  sample container with water to the final sample
level.  Transfer the water to a graduated cylinder, and determine
the final sample volume (Vgoln ).

   5.  If  V____  is less than V__n_ , correct the sample  volume
            soxn^               soj.n •
(V oln) by using Equation 5-1:
                                                     ''"'  /•••

-------
                                              Section No. 3.15.5
                                              Date April 16, 1986
                                              Page 2
                                                       o
              V
               soln
          = V
                               V
             soln
soln,
Equation 5-1
where:
                               V
                     soln^
  V
   soln
   V
    soln
sample volume to be used for calculations,  ml,

volumetric flask volume, ml,
  V  . . ,«? initial sample volume placed in sample container, ml,
   SOJ-ni   and

  V      = final sample volume removed from container, ml.
   soj.n *.
    6.  Both the corrected  and uncorrected values should be sub-
mitted in the test report to the Agency.

5.1.2  Permanganate  Precipitation  and  Filtration -  After  the
required 36-hour conversion period for the sample has elapsed and
the sample container has been checked for sample loss, the sample
can  be quantitatively transfered to a 1-liter volumetric  flask.
(If the  correction  for  sample  loss has already been made, the
sample should already  be  in  a  1-liter volumetric flask.)  The
procedure  for  precipitating  the  excess  permanganate   is  as
follows:
                                                        O
    1.  Dilute the sample in a 1-liter  volumetric
to volume with reagent water, and mix well.
                                         flask 
    2.  Take a 50-ml aliquot  (va) °f the sample from the 1-liter
volumetric flask, and transfer tfie aliquot to a 250-ml Erlenmeyer
flask  containing  a  Teflon-coated  stirring bar.   If  the  N0_
concentration is low, a 100-ml aliquot may
the instrument response.
                                 be  taken to increase
    3.  Stir,the sample as fast as possible without splashing any
of the sample out of the flask.

    4.  Add a 5% H202  solution  in  5-ml portions while stirring
until the permanganate color disappears.

    5.  Stop  stirring   and  allow  the  precipitated  manganese
dioxide  to  settle.   If the solution is clear, then enough H20_
has  been  added.   If the permanganate  color  persists  in  rhe
solution, then continue the H2O2  addition in 5-ml portions until
a clear solution is produced after settling.

    6.  Assemble  the Buchner funnel and filter flask.  The spout
of the Buchner funnel may be  fitted  with  a  length  of  Teflon
tubing to minimize the  probability  of sample loss by aspiration
during filtration.
                                                        O

-------
I
                                              Section No. 3.15.5
                                              Date April 16, 1986
                                              Page 3

    7.  Place a piece of GF/C filter paper (or an equivalent type
of filter paper)  in  the  Buchner  funnel.   Wet  the paper with
water, and seal the filter by applying a vacuum to the flask.

    8.  Quantitatively  transfer the precipitated sample solution
to  the  filter, and filter the solution.   Wash  the  Erlenmeyer
flask and the solid material on the filter with water four times,
and collect the washings with the filtered solution.

    9.  Quantitatively  transfer  the filtered solution from  the
filter flask to a 250-ml volumetric flask (V.).  Dilute to volume
with water.

    10.  Prepare a reagent blank by repeating  steps  2 through 9
on  a  diluted  sample  of  the  alkaline-permanganate  absorbing
solution.  Dilute 60 ml of the absorbing solution to  100 ml with
water, and use 50 ml in step 2.

5.2 Sample Analysis by Ion Chromatography

    For Method 7D, the  basic components and the operation of the
ion chromatograph are the same as for Method 7A.  A discussion of
the ion chromatograph can be found  in  Section  3.14.2 of Method
7A.  The analyst should be familiar  with  the  operator's manual
for his particular ion chromatograph system.   In  this  section,
the  preparation  of calibration standards, the  use  of  quality
assurance audit samples,  the  analysis  procedure,  and the data
reduction and reporting are described.

5.2.1 Preparation  of Calibration Standards - The accuracy of the
ion  chromatographic   analysis,  as  in  any  analysis,  depends
directly on  the  accuracy of the prepared calibration standards.
The  use  of proper pipetting procedures, described in Method 7A,
Section 3.14.5, and a properly  dried, reagent grade standard are
necessary to obtain  quality  results  from  the  analysis.   The
preparation of the NO«  calibration standards is as follows:

    1.  Dry approximately 15 g of potassium nitrate  (KNO3) in an
oven  at 105  to 110 C for 2 hours.  (Sodium nitrate can also  be
used provided the difference  in the formula weight is considered
in the subsequent calculations.)  Allow the dried KNO^ "to cool to
room temperature in a desiccator before weighing.

    2.  Calibrate  an  analytical  balance  with  a  5-g  Class-S
calibration  weight  and  a  10-g Class-S calibration  weight  to
within  2 mg.  Accurately weigh 9 to 10 g of dried KN03 to within
0.1 mg.

    3.  Dissolve  in  reagent  water,  and dilute to 1 liter in a
Class-A volumetric flask.  Calculate the exact N03~ concentration
using the following formula:

-------
o
                                              Section No. 3.15.5
                                              Date April 16, 1986
                                              Page 4


        vg NO ~/ml = g of KNO- x 103  62'01          Equation 5-2
             J               d        101.1

The stock standard solution  should  be  stable  for  2 months if
precautions, such as refrigeration,  are  used  to prevent decom-
position by nitrate-utilizing microorganisms.

    4.  Prepare a fresh working standard solution for each set of
analyses  by  pipetting  5  ml  of stock standard solution into a
200-ml Class-A volumetric flask.  Dilute to volume with water.

    5.  Prepare  a  series of four calibration standards from the
fresh working standard solution.  Pipet 1.0 ml,  3.0  ml, 5.0 nl,
and 10.0 ml into  a  series  of  four  100-ml  Class-A volumetric
flasks.  Dilute to volume with reagent water.   The concentration
of the calibration  standards  made  from  a  9.7823 g KNO-/liter
(6000 yg NO ~/ml) stock standard solution would be 1.5, 4.5, 7.5,
and 15.0 yg NO- /ml.

The calibration  standard  concentrations cited above are used in
the example employing  Figure  5.1,  the analytical data form for
analysis of calibration standards.

    The  calibration  standards   for  nitrite  quantitation  are  (]
prepared when Method 7D is used for  relative accuracy testing of  \	J
continuous emission monitors.  A stock N02~ standard  solution is
(1)  prepared  with NaN02 of known purity or (2) analyzed  before
use.  Do not oven dry the NaN02.   Dissolve  52.5  mg of NaN02 in
water and dilute  to volume in a 250-ml Class-A volumetric flask.
A  series of four calibration standards with NO2~  concentrations
of 1.4, 4.2, 7.0, and 14.0  g N02~/ml  are  prepared by pipetting
1.0, 3.0, 5.0, and 10 ml of stocR N02~_standard into  four 100-nl
Class-A  volumetric  flasks.   The N02" calibration standards are
diluted to volume with water.

5.2.2  Quality Assurance Audit Samples - The accuracy of the cal-
ibration standards can be assessed by analyzing  nitrate standard
solutions prepared  by  an outside laboratory with the concentra-
tions unknown to the analyst.  For making  compliance  determina-
tions, a set of two Quality  Assurance Audit Samples are obtained
from  the U. S. Environmental  Protection  Agency,  Environmental
Monitoring Systems Laboratory, Quality Assurance Division, Source
Branch, Mail Drop 77A, Research  Triangle  Park,  NC 27711.   (The
analyst  should  notify  the  Quality Assurance  Officer  or  the
responsible enforcement agency at least 30 days in advance of the
need  for quality  assurance  samples.   The  analyst  must   also
specify that the quality  assurance  samples  are for Method  7D.)
The concentrations of the quality assurance samples determined by
the  analyst  must be within 10% of the actual concentrations of
the same samples.
  o

-------
Plant

Date
rrcna.  re
                          PU-h
                                        Location
                                    Section No. 3.15.5
                                    Date April 16, 1986
                                    Page 5
                                    /\Jo .   3
          3//6>
                                        Analys t
                            '.  'S-ft/ns
Standard
identifier
Std 1
Std 2
Std 3
Std 4
Standard
concentration (x)
(yg/ml N03 )
AS-
4..T
7.ST
/f.d
Insl
peak
1
20
££T
11
m
b rumen
heigh
2
ZO
&
  7
                                mm or area count

                                  yg NO ~/ml

   x = standard concentration (yg NO '/ml) = 	A_
    m = calibration curve slope
    b = I = intercept term (mm or area count)  = —().

Predicted Standard Concentration (P)

    P (u  NO ~/ l^ - ^verage Instrument Response (y)  - Intercept  (I)
            •*            ,   Calibration Curve  Slope (m)
P (for first standard) =
= (
                                                  )  =
                                                                 yg NO-"/ml
                                    /3. 6^/75"
Deviation

    Deviation (%)  = P (US NO^/ml) - x (yg NO^/ml)
                              x fo g NO ~/mL)
   Deviation
   (of first set   /   / 5-4
   of standards) =
                                               loo? =
                               /.5
    Figure 5-1-   Analytical data form for analyses of calibration standards.

-------
o
                                              Section No. 3.15.5
                                              Date April 16, 1986
                                              Page 6

5.2.3.  Ion Chromatographic Analysis - The selection of  the  ion
chromatographic   conditions   depends   on  the  particular  ion
chromatograph system available to the analyst.   The selection of
eluents for ion chromatography depends on the method of detection
used.  For suppressed ion chromatography the following conditions
have been used successfully:

   1. A 0.003M  NaHC(Xj/0.0024M Na2CO3 eluent solution is prepared
by dissolving 1.008 g of NaHCCXs and 1.018 of NaoCO^ in water  and
diluting to 4 liters.         *                   *

   2. The  full-scale  detection range is set at 3  vMHO,  and  a
0.5-ml sample loop is used.

   3. A flow rate of  2.5  ml/min  gives a NO ~ retention time of
approximately 15 minutes depending on the type of column used.

    Non-suppressed ion chromatography  and  ion-pairing chromato-
graphy may  also be used provided baseline separation of NO3~ and
SO^  separation and detection of N02~ are  obtained  (see  Figure
5.2).  Packed-bed  suppression  columns  are  not recommended for
quantifying  NO2~  when  using  Method  7D  for relative accuracy
testing.

    The  recommended  procedure   for   the  ion  chromatographic
analysis is as follows:

   1. Establish a stable baseline.  Inject a samgle of water, and
observe the chromatogram to  see whether any NCU  elutes.   Repeat
the   water  injection  until  N03   is  not_ ooserved   on  the
chromatogram.  If, after 5 injections, a N03~ peak is still  seen,
the water source should be checked for contamination.

   2.  Inject  samples  in  the   following  order:   calibration
standards, reagent blank,  field  samples, calibration standards,
reagent  blank,  field  samples,   calibration   standards.   The
injection volumes for all the standards and samples should  be the
same.

   3. The  chromatograms  should be documented  with  the   sample
identification,  injection  point,  injection   volume,   nitrate
retention time, eluent flow rate, detector  sensitivity  setting,
and recorder chart speed.

   4. Manually measure the N03~ peak  height or determine the N03
peak area with an electronic integrator.

5.2.4  Data  Reduction  and  Reporting  - The details of the data
reduction  procedure are discussed in Section 3.15.6.  The  proce-
dures  for calculating a response  factor  from  the  calibration   /"N
standards by linear regression  and  for calculating the %  devia-    \	)
tion on each standard from the predicted value are as follows:
o

-------
                                              Section No. 3.15.5
                                              Date April 16, 1986
                                              Page 7
                                            Flow Rate: 1.5 ml/zain
                                       Detector: 30  S full  scale
                                                 Injection:  50 vl
                                                    3.3 minutes
                    Inject
Figure 5.2.   Example of chromatogram having adequate documentation.

-------
                                              Section No.  3.15.5
                                              Date April 16,  1986
                                              Page 8

    1.  Use the analytical  date  form  (see Figure 5.1) for cal-
culating the linear regression equation based  on the calibration
standards.

    2.  Record the calculated  concentrations  for the four cali-
bration standards (x) on the data sheet.   Determine  the average
value  for  the instrument response (y) for NO,," (peak height  or
area  under the peak) from the three determinations for  each  of
the four calibration standards.

    3.  Plot the average  values  for the instrument response for
the  calibration  standards  against the corresponding calculated
concentrations of the calibration standards.  Draw a smooth curve
through the points without  forcing  the curve through zero.  The
curve should be linear.

    4.  Determine the slope (m) and the intercept term  (b  or I)
for the linear calibration  curve  by  linear  regression.   Many
scientific   calculators   are   capable   of  performing  linear
regression.

    5.  Calculate  the  predicted  standard concentration (P) for
each calibration standard using the following equation:

                                                     Equation 5-3

  P( a/ml NO ~)   Average Instrument Response (y) - Intercept (I)
   \v g/     £ )           Calibration Curve Slope (m)

    6.  Calculate  the  percent  deviation  of  each  calibration
standard  (x)  from  the  predicted  value  using  the  following
equation (optional):

                                                    Equation 5-4

    % Deviation = P (ug N03 /ml) -. x (ug N03 ml) ^ 1QO

                           x (vig NO3~/ml)

    If any standard deviates from the standard curve by more than
+7%, the problem should be investigated.

    The  concentration  of the field samples, the reagent  blank,
and  the quality assurance samples are  calculated  by  the  sane
procedure  used  to  calculate   the  predicted  values  for  the
calibration standards.  Use the data form shown in Figure 5.3 for
the analysis of field samples.  The procedure is as follows:

    1.  Determine the instrument response  factor  for the sample
and  calculate  the  sample  concentration  using  Equation  5-3.
Calculate  the  average  value for the two determinations made on
each sample.
                 o
                 o
43'

-------
                                                              Section No.  3.15.5
                                                              Date .April  16. 1986
                                                              Page 9
Date samples received   3 /l(f I&4'  Date samples analyzed   3 / 16 / &4

Plant   Acme  Porter   Tlswrb _  Run number (s) AP~ I. 2..  £

                                                .  S-f-e/n s
                                                  ~'     ~~~
Location
     /f.7""
    -
                                      Analyst
                             .
                 ~        <-j                     —   j-ui- ~'     -~~~    -~
  Calibration curve slope (m)  /3.6/75^ Intercept term  (I)  — £>,
Field
sample
number
AH
Af~l
AW
Field
Blank
Analysis
number
1st
2nd
1st
2nd
1st
2nd
1st
2nd
Instrument
response (y)
(mm or area counts)
7f /**/*?
78wm
6>4-ww
(p2.MH[
72 turn
~JO wn\
5~ww
S~Kt4\
Concentration of
analysis sample
(Vg/ml N03 )
^.B
.577
1-.7
. 4-.(r
573
5:^
0.51
0.31
Average
Concentration of
analysis sample
(vg/ml N03 )
S= 5~7S-
s= f.^r
S = ^Z^
B= A3?
Deviation
(^)
0*67
I.I
6.9S~
A/A
Concentration of
Analysis Sample
(yg N03"/ml)

Concentration
(of first sample)
Deviation
  (*)

Deviation
(of first
standard set)
Instrument Response (y) - Intercept  (I)
     Calibration Curve Slope (m)
 Sample Concentration - Average Concentration    IQQ%
           Average Concentration
                         -  (
                 >
       Figure 5.3.  NO  laboratory data form for analyses  of field  samples.

-------
                                              Section No.  3.15.5
                                              Date April 16,  1986
                                              Page 10

    2.  Calculate  the  percent deviation  of  the  concentration
measured for each individual  sample  from  the  average  of  the
concentrations  measured  for the  duplicate  samples  using  the
following equation:

                                                     Equation 5-5

% Deviation = Sample Concentration - Average Concentration   1QO
                         Average Concentration

    The percent deviation for a sample must  be  within 5% of the
average value before the analysis can be considered valid.

    The  data  reduction  procedures  described  above  for  N03~
analysis  can  be used for N0«  analysis when using Method 7D for
relative accuracy testing of continuous emission monitors.

    The  main  parameters  of  the analytical procedures  may  be
checked  during  or  after  the  analysis,  using  the   posttest
operations form (Figure 5.4).
                                                                  o
                                                                   o
                                                    'JO

-------
                                              Section No. 3.15.5
                                              Date April 16, 1986
                                              Page 11
Reagents
Potassium nitrate dried at 105° to 110°C for a minimum
  of 2 hours before use?
Stock standard solution (potassium nitrate) less than 2 months
  old? 	S	

Sample Preparation
Has liquid level noticeably changed?* 	/vo	
  Original volume 	  Corrected volume 	

Analysis
Standard calibration curve prepared?* 	"_	__
All calibration points within 7 percent of linear calibration
  curve (optional) ?
Reagent blanks made from absorbing solution?
Same injection volume for both standards and samples? _
Duplicate sample values agree within 5 percent of their mean?
Audit sample analytical results within 10 percent of true value?
All analytical data recorded on checklist and laboratory form?
* Most significant items/parameters to be checked.
                Figure 5.4.  Posttest operations.

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                                                               Section 3-15-5
                                                               Date April 16, 19=6
                                                               Page 12
                     Table 5.1.  ACTIVITY MATRIX FOR SAMPLE ANALYSIS
                                                              o
Characteristics
Acceptance Limits
Frequency and method
   of measurement
Action if
requirements
are not met
Sample Preparation

1.   Conversion
      time
2.  Sample loss
3.   Permanganate
      precipitation
    Permanganate
      filtration
 36 hour minimum
 Noticeable amount
 Absence of purple
 permanganate color
 Absence of solids
 in the filtrate
 Determine sample age
 Compare sample level
 to mark on container
Between each 5 *&•
portion of 5% ^J^?
solution

After filtration is
complete
Hold sample in
container for 36
hours miniinin time

Correct by proce-
dure in Section
5.1.1

Continue adding
5 ml portions
of 5% H0
                          Refilter
                O
Calibration Stan-
 dards Preparation

1.  ACS grade KNCL
 15 g dry KNO_
 Oven dry at 105  to
 110°C for 2 hours;
 cool in desiccator
2.  Stock standard
      solution
3.  Calibration
     standards
 9 to 10 g of KNO.
 accurately weighed
 to 0.1 mg; dilute
 to 1 liter; store
 refrigerated
 Standard range to
 cover sample range;
 maximum allowed
 deviation of indi-
 vidual standard
 from the predicted
 value is +J%
 (optionalj
 Calibrate analytical
 balance
 Use recommended volumes
 of stock standard solu-
 tion; calculate devia-
 tion (optional) using
 Equation 5-4
High bias will
occur if stan-
dard contains
moisture; redry

KN°3
Biases will occur
with poor pipet-
ting or improper
storage;
remake standard
Invalid  analysis;
remake and rerun
calibration
standards
(continued)
                                                                                    O

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                                                                Section  3.15.5
                                                                Date April  16, 1986
                                                                Page 13
Table 5.1.  (continued)
Characteristics
                     Acceptance Limits
                                          Frequency and  method
                                             of measurement
                                                                   Action if
                                                                   requirements
                                                                   are not met
Ion Chromatograph
 Analysis

1. Sample injection
    device
2. Sample analysis
3.  Chromatogram
     documentation
k. Quality
    assurance
                     Absence of KNO_
                     on chromatogram of
                     water injection

                     Individual sample
                     replicates within
                     5% of average

                     Include sample
                     identi fication,
                     injection point,
                     injection volume,
                     N0.,~ retention
                     time, eluent flow
                     rate, detector
                     sensitivity setting,
                     and chart speed

                     Analytical results
                     must be within 10%
                     of actual value
                                          Inject reagent water
                                          up to four times
                                          Calculate deviation
                                          using Equation 5~5
                                          Visually check
                                          Report results to
                                          agency with sample
                                          identification
                                                                 Check water source
                                                                 for contamination
                                                                 Invalidate analysis
                                                                 reanalyze samples
                                                                 Supply missing
                                                                 information
                                                                 Invalidate analysis;
                                                                 repeat preparation
                                                                 of sample; prepare
                                                                 new standards

-------
o
o
o

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                                              Section No. 3.15.6
                                              Date April 16, 1986
                                              Page 1
6.0  CALCULATIONS
    Calculation errors due to procedural or mathematical mistakes
can be a large component of total system error.  Therefore, it is
recommended that each  set  of  calculations be repeated or spot-
checked, preferably by a team member other  than the one who per-
formed the original calculations.  If  a  difference greater than
typical round-off error is detected,  the  calculations should be
corrected.  A computer program is advantageous in reducing calcu-
lation errors.  If a standardized  computer  program is used, the
original data entry should be checked,  and  if  differences  are
observed, a new computer run should  be  made.   Table 6.1 at the
end of this section  summarizes  the quality assurance activities
for calculations.

    Calculations  should  be  carried  at least one extra decimal
figure  beyond  that  of the acquired data, and should be rounded
after final calculation to two significant digits for each run or
sample.  All rounding of numbers  should  be  performed in accor-
dance with the ASTM 380-76 procedures.  All calculations are then
recorded on a form such as the ones  shown  in  Figure  6.1A  and
6.IB, following the nomenclature list.

6.1  Nomenclature

    The following nomenclature is used in the calculations:
    V
     m
    Y

    P
     bar

     'std
     m
     'std
    V
     m(std)
dry gas volume as measured by the dry gas meter,
dcm (dcf),

dry gas meter calibration factor, dimensionless,

barometric pressure, mm (in.) Hg,

standard absolute pressure, 760 mm (29.92 in.) Hg,

average dry gas meter absolute temperature, °K (°R),

standard absolute temperature, 293°K (528°R),

dry gas volume measured by the dry gas meter
corrected to standard conditions, dscm (dscf).
    S

    B

    m

    C


    X
analysis of sample, yg
                         w

analysis of blank, vg NO3~/ml,

mass of NO,, as NO- in sample, yg,
          X      ^

concentration of NO  as N09, dry basis, mg/dscm
(Ib/dscf), and     x

    correction factor.

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                                              Section No.  3.15.6
                                              Date April  16,  1986
                                              Page 2
6.2  Calculations
                                                                   o
    The following are the equations used with example calculation
forms (Figures 6.1A and 6.IB) to calculate the  concentration  of
nitrogen oxides in the samples.

6.2.1  Sample Volume - Calculate the sample volume on a dry basis
at standard conditions (760 mm (29.92 in.) Hg and 293°K (528  R)
using Equation 6-1.

                        T     p                v  p  Equation 6-1
    Vm(std) =  Vm *X^ Y   td   par =  K! (X) Y  m  bar

where:                  Tm    ?std                Tm

     X  =  correction factor for CO2 collection,    100	
                                                 100 - %CO2 v/v ,
     K., =  0.3858    K  for metric units, or
                   mmHg

     K. =  17.64   °R   for English units.
                  in. Hg

6.2.2  Total  g NOg Per Sample - Calculate the  total  yg  of N0~
per sample using Equation 6-2.

             t*   n\ o*n v 100° v 46.01   o-7-in fa   n\
        m  = (S - B) ZoU x 	 x 	 = o71O (S - B)

                            50    62.01

                                                     Equation 6-2
where:

      250  =  volume of prepared sample, ml,

    46.01  =  molecular weight of NO2~,

    62.01  =  molecular weight of N03~,

      1000  =  total volume of KMnO. solution, ml, and

       50  =  aliquot KMn04 / NaOH solution, ml.


6.2.3  Sample  Concentration - Calculate the sample concentration
on a  dry basis at standard conditions using Equation 6-3.
              C = K
                                                                    o
                      V , .  , x                        Equation 6-3
where:                 m(std)   .
             _q
    K0  =  10   mg/ug for metric units, or                           — ^
                                                                    O
    K2  =  2.205 x 10"9 Ib/yg for English units.                    ^-^
                                                  /&

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                                               Section No.  3.15.6
                                               Date April  16,  1966
                                               Page 3
                           Sample Volume


                     dcf,  Y=  /. 0  2-  O, x =  I.I
 bar  =  2^ 9_-_4^ J_ in.  Hg,  T  =  5~
Vm(std)  =  17-64  x Y  m  bar = -L'-L — -~L dscf         Equation 6-1

                         Tm


                     Total yg N02 Per Sample


     <""  7  <~              r>  2 ci



m =  3710  (S - B)  =_/.jf._6__^__(£_vgof N02           Equation 6-2



                           Sample Concentration


              — Q     m         *2   G  /  £)      —*?
C = 2.205  x 10 y	   = _£.-__/ _"_ &_ x 10 °  Ib/dscf

                    m(std)                              Equation 6-3



                       Sample Concentration in ppm


ppm NO.,  =  8.375  x  10  C =     332-  ppm NO.,          Equation 6-4
      £t                      '~ ' ' ~ l-r.-TB- J 	        £t
  Figure 6.1A.  Nitrogen oxide calculation form  (English  units).
                                                /•'V7

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                                               Section No- 3.15.6

                                               Date April 16, 1986
                                               Page 4
                            Sample Volume
                                                                     o
vm = 0.0 .2 _Z_ 0_ l_ ]_  m3,  Y = _/_._£ _£_ 0_, x = J_.J_ ±_  4_.
"bar ~ -i- _L _£.
                       '  Tm =
                                          'K
Vm(std) = °-3858  x Y Vin Pbar = 0.0 ^ J_

                          m •
                                                dscm     Equation 6-1
                       Total vg N02 Per Sample
S =  _. _   _ v g/ml ,    B = _
                                     g/ml
m = 3710  (S  -  B)
                                                         Equation 6-2
C = 10
      '3
           m(std)
                        Sample Concentration
                            _>__ mg N02/dscm
Equation 6-3
                                                                     O
                    Sample Concentration in ppm
ppm N0« = 0.5228  C =     332- ppm N00
      «                ~'      "^^          ^
                                                         Equation 6-4
  Figure  6.IB.   Nitrogen oxide calculation form  (metric  units).
                                                                      O

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                                    Section No.  3.15.6
                                    Date October 23,  ig85
                                    Page 5
Table 6.1.  ACTIVITY MATRIX FOR CALCULATIONS
Charac teris tics
Sample volume
calculation
Sample mass
calculation
'Sample concen-
tration
Calculation
check
Document and
report re-
sults
Acceptance limits
All data available;
calculations correct
within round-off error
As above
As above
Original and checked
calculations agree
within round-off error
All data available;
calculations correct
within round-off error
Frequency and method
of measurement
For each sample, exam-
ine the data form
As above
As above
For each sample, per-
. form independent cal-
culations
For each sample, exam-
ine the data form
Action if
requirements
are not met
Complete the
data, or void
the sample
As above
As above
Check and
correct all data
Complete the
data, or void
the sample
                                                  ,
                                                  V.

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o
o
o

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                                                   Section No. 3.15.7
                                                   Date July 1, 1986
                                                   Page 1
 7.0  MAINTENANCE
    The normal use  of emission-testing equipment subjects it to cor-
rosive gases, extremes in temperature, vibration, and shock.  Keeping
the equipment in good operating order over an extended period of time
requires knowledge of the equipment and  a  program  of routine3main-
tenance  which  is  performed quarterly or after 2830 L (100 ft )  of
operation, whichever is greater.  In addition to the quarterly  main-
tenance,  a  yearly  cleaning of the entire meter box is recommended.
Maintenance procedures for the various  components  are summarized in
Table 7.1  at  the  end of the section.  The following procedures are
not required, but are recommended to increase the reliability  of the
equipment.
    In the present commercial sampling train, several types of  pumps
are used; the  two'  most  common are the fiber vane pump with in-line
oiler  and  the  diaphragm  pump.   The  fiber  vane  pump requires a
periodic check of the oiler Jar.  Its contents should be translucent;
the oil should be changed if not translucent.  Use the oil  specified
by the manufacturer.   If  none is specified, use SAE-10 nondetergent
oil.   Whenever the fiber vane pump  starts  to  run  erratically  or
during the yearly disassembly, the head  should  be  removed  and the
fiber  vanes  changed.   Erratic  operation of the diaphragm pump  is
normally  due  to  either  a  bad diaphragm (causing leakage)  or  to
malfunctions of the  valves,  which  should  be  cleaned  annually by
complete disassembly.

7.2  Dry Gas Meter

    The dry gas meter should be checked for excess oil  or  corrosion
of the components by  removing  the  top  plate  every 3 months.  The
meter should be  disassembled  and all components cleaned and checked
whenever  the  rotation  of the dials is erratic, whenever the  meter
will  not  calibrate  properly over the required flow rate range, and
during the yearly maintenance.

7.3  Rotameter

    The rotameter should be disassembled and cleaned according to the
manufacturer's  instructions using only recommended  cleaning  fluids
every 3 months or upon erratic operation.

7.4  Sampling Train

    All  remaining  sampling  train  components  should  be  visually
checked every  3  months  and  completely disassembled and cleaned or
replaced yearly.  Many items, such as quick  disconnects,  should  be
replaced   whenever  damaged  rather   than   checked   periodically.
Normally,  the best  procedure  for maintenance in the field is to use
another entire unit such as  a  meter  box,  sample box,  or umbilical

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                                                   Section No.  3.15.7    (]
                                                   Date July 1,  1986     V_/
                                                   Page 2

cord (the  hose  that  connects  the sample box and meter box)  rather
than replacing individual components.

7.5  Ion chromatograph

    Maintenance activities and schedules  for  ion chromatographs are
make and model  specific.   It  is  therefore  recommended  that  the
analyst  consult  the  operator's manual for instructions relative to
maintenance practices and procedures.

    Guard columns, while not required,  are  recommended for use with
the ion chromatograph in order to extend column lifetime.
                                                                         o
                                                                          o

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                                                                Section No. 3.15.7
                                                                Date July 1, 1986
                                                                Page 3
            Table 7.1.  ACTIVITY MATRIX FOR EQUIPMENT MAINTENANCE CHECKS
  Apparatus
 Acceptance limits
Sample train
 control con-
 sole
Fiber vane pump
Diaphragm pump
Dry gas meter
Rotameter
Sampling train
Ion chroma-
 tograph
No erratic behavior
In-line oiler free of
leaks
Leak-free valves
functioning properly
No excess oil, corro-
sion, or erratic rota-
tion of the dial
Clean and no erratic
behavior
No damage
See owner's manual
Frequency and method
   of measurement
Routine maintenance
performed quarterly;
disassemble and clean
yearly
Periodically check
oiler jar; remove
head and change fiber
vanes
Clean valves during
yearly disassembly
Check every 3 no. for
excess oil or corrosion
by removing the top
plate; check valves and
diaphragm yearly and
whenever meter dial runs
erratically or whenever
meter will not calibrate
Clean every 3 no. or
whenever ball does not
move freely
Visually check every
3 mo.; completely dis-
assemble and clean or
replace yearly
See owner's manual
Action if
requirements
are not met
Replace parts
as needed
Replace as
needed
Replace when
leaking or mal-
functioning
Replace parts
as needed, or
replace meter
Replace
If failure
noted, use an-
other entire
meter box,
sample box,
or umbilical
cord
See owner's
manual

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o
o
o

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       Section  No.  3.15.10
       Date  July  1,  1986
       Page  1
  10.0    REFERENCE  METHOD*,**

  Method TO—Determination of Nitrogen
  Oxide Emission* From Stationary Sources

  A tkaline-Pemanganate/Ion
  Chromatographic Method

   1. Applicability. Principle. Interferences.
  Precision. Bias, and Stability.
   1.1  Applicability. The method is
 •applicable to the determination of NO,
  emissions from fossil-fuel fired steam
  generators, electric utility plants, nitric acid
  plants, or other sources as specified in the -
  regulations. The lower detectable limit is
  similar to that for Method 7C. No upper limit
  has been established however, when using
  the recommended sampling conditions, the
  method has been found to collect NO,
 emissions quantitatively up to 1782 mg/NO,/
 m». as NO, (932 pm NO.).
  ' 12  Principle. An integrated gas sample is
 extracted from the stack and collected in
 alkaline-potassium permanganate solution;
 NO, (NO 4-NOi) emissions are oxidized to
 NO,-, Then NO>- is analyzed by ion
 chromatography.
   1.3  Interferences. Possible interferences
 are SOj and NH». High concentrations of SOj
 could interfere because SO, consumes MnO«-
 (as does NO,) and. therefore, could reduce
 the NO, collection efficiency. However, when
 sampling emissions from a coal-fired electric
 utility plant burning 2.1-percent sulfur coal
 with no control of SO, emission*, collection
 efficiency was not reduced. In fact.
 calculations show that sampling 3000 ppm
 SO, will reduce the MnO.- concentration by
 only 5 percent if all the SO, is consumed in
 the first impinger.
  NHj is slowly oxidized to N0»- by the
 absorbing solution. At 100 ppm NH» in the
 gas stream, an interference of 6 ppm NO, (11
mg NOs/m") was observed when the sample
was analyzed 10 days after collection.
Therefore, the method may not be applicable
to plants using NH> injection to control NO,
emissions unless means are taken to correct
the results. An equation has been developed
to allow quantitation of the interference and
is discussed in Citation 4 of the bibliography.
  1.4  Precision and Bias. The method does
not exhibit any bias relative to Method 7. The
within-laboratory relative standard deviation
for a single measurement was approximately
6 percent at 200 to 270 ppm NO,.
  13  Stability. Collected samples are stable
for at least 4 weeks.
  2. Apparatus.
  2.1   Sampling and Sample Recovery. The
sampling train is the same as in Figure 7C-1
of Method 7C. Component parts are the same                                  '    "
as in Method 7C. Section'2.1.


  *Method  7C  is  reproduced  in  this  section  in  addition to Method  7D
  since  the  latter   refers    extensively   to Method  7C  and Method  7C
  is  not  reproduced  elsewhere  in  this  Handbook.


  **  Federal  Register,  Volume  49,  No.  189,   September  27,   1984.
                    t

                                                                                    "~"i               ^  "
   2.2  Sample Preparation and Analysis,
   2.2.1  Magnetic Stirrer. With 25- by 10-mm
 Teflon-coated stirring bars.
   2^2  Filtering Flask. 500-ml capacity with
 sidearm.
   2^.3  Buchner Funnel. 75-mm ID. The
 spout equipped with a 13-mm ID by 90-mm
 long pjece of Teflon'tubing to minimize
 possibility of aspirating sample solution
 during filtration.
   2^.4  Filter Pnper. Whatman GF/C. 7.0-cm
 diameter.
   2.2.5  Stirring Rods.
        Volumetric Flask. 250-ml.
        Pipettes. Class A.
        Erlenmeyer Flasks. 250-ml.
        Ion Chromatograph. Equipped with
 an anion separator column to separate NOt-,
 a H* suppressor, and*necessary auxiliary
 equipment. Nonsuppressed and other forms
 of ion chromatography may also be used
 provided that adequate resolution of NOj- is
 obtained. The system must also be able to
 resolve and detect NO^.
  3. Reagents.
  Unless otherwise indicated, all reagents
 should conform to the specifications
 established by the Committee on Analytical
 Reagents of the American Chemical Society,
 where such specifications are available;
 otherwise,  use the best available grade.
  3.1  Sampling.
  3.1.1   Water. Deionized distilled to
 conform to ASTM specification D 1193-74.
 Type 3 (incorporated by reference—see
 § 60.17).
  3.1.2   Potassium  Permanganate. 4.0 Percent
 (w/w). Sodium Hydroxide. 2.0 Percent (w/w).
 Dissolve 40.0 g of KMnO, and 20.0 g of NaOH
 in 940 ml of water.
  3.2  Sample Preparation and Analysis.
  3.2.1   Water. Same as in Section 3.1.1.
  3.2J?   Hydrogen Peroxide. 5 Percent. Dilute
 30 percent HiO, 1:5 (v/v) with water.
  3.2J   Blank Solution. Dissolve 2.4 g of
 KMnO. and 1.2 g of NaOH in 63 ml of water.
 Alternatively, dilute 60 ml of KMnO./NaOH
 solution to  100 ml.
  3.2.4   KNO» Standard Solution. Dry
 KNOj at 110 ' C for 2 hours, and cool in a
desiccator.  Accurately weigh 9 to 10 g of
KNO> to within 0.1 mg. dissolve in water, and
dilute to 1 liter. Calculate the exact NO,-
concentration from the following relationship
   NOi-/m)*g of KNO, XlO'x •
62.01

101.10

-------
 This solution it liable for 2 months without
 preservative under laboratory conditions.
   3.2.5  Eluent, 0.003 M NaHCOj/0.0024 M
 NaiCO). Dissolve 1.008 g NaHCOj and 1.018 g
 NaiCOj in water, and dilute to 4 liters. Other
 eiuents capable of resolving nitrate ion from
 sulfate and other species present may be
 used.
   3.2.6  Quality Assurance Audit Samples.
 This is the tame as in Method 7, section 3J.9.
 When requesting audit samples, specify that
 they be in the appropriate concentration
 range for Method 7D.    '-' > v-\ .-
   4. Procedure.
   4.1  Sampling. This is the tame es in
 Method 7C. Section 4.1.
   4.2  Sample Recovery. This is the tame as
 in Method 7C. Section 4.2.
   4.3  Sample Preparation for Analysis. Note
 the level of liquid in the sample container,
 and determine whether any sample was lost
 during shipment. If a noticeable amount of
 leakage has occurred, the volume lost can be
 determined from the  difference between
 initial and final solution levels, and this value
 can then be used to correct  the analytical
 result. Quantitatively transfer the contents to
 a 1-liter volumetric flask, and dilute to
 volume.

   Sample preparation can be started 36 hours
 after collection. This time is necessary to
 ensure that all NOr- is converted to NOj-.
 Take a 50-ml aliquot of the sample and
 blank, and transfer to 250-ml Erlenmeyer
 flasks. Add a magnetic stirring bar. Adjust
 the stirring rate to as  fast a rate as possible
 without loss of solution. Add 5 percent
 HiO» in increments of approximately 5 ml
 using a 5-ml pipette. When the KMnCX color
 appears to have been removed, allow the
 precipitate to settle, and examine the
 supernatant liquid. If the liquid is clear, the
 HjOj addition is complete. If the
 KMuO* color persists, add more HjOi, with
 stirring, until the supernatant liquid is clear.
 Note.—The faster the stirring rate, the less
 volume of HjOj that will be required to
 remove the KMnO..) Quantitatively transfer
 the mixture to a Buchner funnel contaiing
GF/C filter paper, and filter the precipitate.
The spout of the Buchner funnel should be
equipped with a 13-mm ID by 90-mm long
piece of Teflon tubing. This modification
minimizes the possibility of aspirating sample
solution during filtration. Filter the mixture
into a 500-ml filtering flask. Wash the solid
material four times with water. When
filtration is complete, wash the Teflon tubing.
quantitatively transfer the filtrate to a 250-ml
volumetric flask, and dilute to volume. The
sample and blank are now ready for
NOi  analysis.
   4.4  Sample Analysis. The following
 chromatographic conditions are
recommended: 0.003 M NaHCOi/0.0024 M
 NjuCO, eluent solution. (3.2.5). full scale
 range 3 nMHO: sample loop, 0.5 ml: flow rate,
2,5 ml/rain. These conditions should give a
 NO»- retention time of approximately 15
rnmutes (Figure 7D-1).
                                                                                     Section  No.  3.15.10
                                                                                     Date  July  1,  1986
                                                                                     Page  2
                 »
                               t>
                  TWt.0.

    Fifvn 70-1.  IOT n»»nl»y»» •' • trtMrtt ««•»!•


  Establish a stable baseline. Inject a sample
of water, and determine if any NOr- appears
in the chromatogram. If NO>- is present.
repeat the water load/injection procedure
opproximately five times: then re-inject t
water sample, and observe the
chromatogram. When no N0»- is present, the
instrument is ready for use. Inject calibration
standards. Then inject samples and a blank.
Repeat the injection of the calibration
standards (to compensate for any drift in
response of the instrument). Measure the
NOj peak height or peak area, and determine
the sample concentration from the calibration
curve.
  4.5  Audit analysis. This is the same as in
Method 7. Section 4.4
  5. Calibration.
  5.1  Dry Gas Metering System (DGM).
  5.1.1  Initial Calibration. Same as in
Method 0. Section 5.1.1. For detailed
instructions on carrying out this calibration, it
is suggested that Section 3.5.2 of Citation 3 in
the bibliography be consulted.
  5.1.2  Post-Test Calibration Check. Same
es in Method 6, Section 5.1.2.
  5.2  Thermometers for DGM and
Barometer. Same as in Method 6, Section 5.2
and 5.4, respectively.
  5.3  Calibration Curve for Ion
Chromatograph. Dilute a given volume (1.0 ml
or greater) of the KNO> standard solution to a
convenient volume with water, and use this
solution to prepare calibration standards.
Prepare at least four standards to cover the
range of the samples being analyzed. Use
pipettes for all additions. Run standards as
instructed in Section 4.4. Determine peak
height or area, and plot the individual values
versus concentration in ng NO>-/ml. Do not
force the curve through zero.  Draw a smooth
curve through the points. The curve should be
linear. With the linear curve, use linear
regression to determine the calibration
equation.
                                                   o
O
o

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    6. Calculations.
    Carry out calculation!, retaining at least
   one extra decimal figure beyond that of the
   acquired data. Round off figures after final
   calculation.
    6.1  Sample Volume, Dry Basis. Corrected
   to Standard Conditions. Same as in Method
   7C, Section 6.1.
    6.2  Total figNO. Per Sample.
                                                                                   Section  No.   3.15.10
                                                                                   Date  July 1,   1935
                                                                                   Page  3
                   1000    46.01
 m-(S-B)x250x    -  x
                   50
•3710 (S-BT    (Eq. 7D-1)
 Where:  .
 m—Mass of NO,, as NO,, in sample, fig.
 S—Analysis of sample, fig NOi-/ml.
 B—Analysis of blank, fig NCS-/ml.
 250—Volume of prepared sample, ml.
 46.01—Molecular'weight of NOi-.
 62.01-Molecular weight of NO,-.
 1000-Total volume of KMnO4 solution, ml.
 50-Aliquot KMnO4/NaOH solution, ml.
   6.3  Sample Concentration.
                       m
              C—Ka '
 Where:
 C—Concentration of NO, as NO>. dry basis.
     mg/dr,cm.
 Kj-10-»mg/ng.
 V»t.u>—Dry gas volume measured by the dry
     gas meter, corrected to standard
     conditions, dscm.
   6.4  Conversion Factors.
 1.0ppm NO-1.247 mg NO/m'atSTP.
 1.0 ppm NO,-1.912 mg NOj/m'at STP.
 Ift'-2.832xi0-'m».
   7. Quality Control.
  Quality control procedures are specified in
Sections 4.1.3 (flow rate accuracy) and 4.5
(audit analysis accuracy) of Method 7C.
  &.13ibliography.
  1. Margeson. J.H., W.J. Mitchell, J.C. Suggs,
and M.R. Midgett. Integrated Sampling and
Analysis' Methods for Determining NO,
Emissions at Electric Utility Plants. U.S.
Environmental Protection Agency. Research
Triangle Park. N.C. Journal of the Air
Pollution Control Association. 22.1210-1215.
1982.
  2. Memorandum and attachment form J.H.
Margeson. Source Branch. Quality Assurance
Division. Environmental Monitoring Systems
Laboratory, to The Record. EPA. March 30,
1983. NHj Interference in Methods 7C and 7D.
  3. Quality Assurance  Handbook for Air
Pollution Measurement  Systems. Volume
III—Stationary Source Specific Methods. U.S.
Environmental Protection Agency. Research
Triangle Park. N.C. Publication No. EPA-600/
4-77-027b. August 1977.
  4. Margeson. J.H.. et al. An Integrated
Method for determining NO. Emissions at
Nitric Acid Plants. Manuscript submitted to
Analytical Chemistry. April 19B4.

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                                                               Section  No.  3.15.10
                                                               Date  July  1,  1986
                                                               Page  4
                                                                      o
 Method 7C— Determination of Nitrogen
 Oxide Emissions From Stationary Source*

 Alkoline-Permonfionote/Colorimftric
 Method
  1. Applicability. Principle. Interferences,
 Precision, Bias, and Stability.
  1.1  Applicability. The method ii
 applicable to the determination of NO,
 emissions from fossil-fur;] fired steam
 generators, electric utility plants, nitric acid
 plants, or other sources as specified in the
 regulations. The lower detectable limit is 13
 mg NO./m', as NO, (1 ppm NO.) when
 sampling at 500 cc/min for 1 hour. No upper
 limit has been established: however, when
 using the recommended sampling conditions
 the method has been found to collect NO,
 emissions quantitatively up to 1,702 mg NO,/
 m>. as NO, (932 ppm NO.).
  1.2  Principle. An integrated CBS sample is
 extracted from the stack and collected in
 alkaline-potassium permanganate solution;
NO, (NO+NO,) emissions art oxidized to
NOi- and NOj-. The NOr- is reduced to
N0»- with cadmium, and the NO»- i»
analyzed colorimetrically.
  1.3  Interferences. Possible interferences
are SO, and NH». High concentration* of SO,
could interfere because SO, consumes MnO<-
(as doe* NOJ and, therefore, could reduce
 the NO, collection efficiency. However, when
 sampling emissions from B cout-fired electric
 utility plant burning 2.1-percent sulfur coal
 with no control of SO, emissions, collection
 efficiency was not reduced. In fact.
 calculations show that sampling 3000 ppm
 SO, will reduce the MnO«- concentration by
 only 5 percent If all the SO, is consumed in
 the first impinger.
  NHi is slowly oxidized to NOr- by the
 absorbing solution. At 100 ppm NH» in the
 gas stream, an interference of 6 ppn NO. (11
 mg NOj/m1) was observed when the sample
 was analyzed 10 days after collection.
 Therefore, the method may not be applicable
 to plants using NHj injection to control NO,
 emissions unless  means are taken to correct
 the result*. An equation h«» been developed
 to allow quantitalion of the interference and
 is discussed In Citation 5 of the bibliography.
  1.4  Precision and Bias. The method does
 not exhibit any bias relative to Method 7. The
 within-Laboratory relative standard  deviation
 for a single measurement is 2.8 and Z£
 percent at 201 and 268 ppm NO,, respectively.
  l.S  Stability. Collected  samples are stable
 for at least 4 weeks.
  2. Apparatus.
  2.1  Sampling and Sample Recovery. The
Sampling train is  shown in Figure 7C-1. and
component parts are discussed beJow.
Alternative apparatus and procedures are
allowed provided acceptable accuracy and
precision  can be demonstrated.
O
                                            REiTRicno ORIFICE tutr INCTHT
                                                                         Jure* en.
                                                                        D»WC »u«
                               (   o,  \
                               I GAS urn* y
                                                     SUICE TAMX
                             Figure 7C-1.  tlOx sampling tr»lr
                                                                     O

-------
    2.1.1  Probs. BorosiUcate glus tubing.
  sufficiently heated to prevent water
  condensation and eqcippcd with an to-slack
  or out-slack filter to remove particulate
  matter (a plug of glass wool is satisfactory for
  this purpose). Stainless stetl or Teflon tubing
  may also be used for the probe. (Note*.
  Mention of trade names or specific products
  does not constitute endorsement by the US.
  Environmental Protection Agency.)
    2.1.2  impingers. Three restricted-orifice
  glass impingers. bavins toe specifications
 given in Fixture 7C-2. are required for each
 sampling train. The impingers must be
 connected in series with leak-free plait
 connectors. Stopcock grease may be used, if
 necessary, to prevent  leakage. (The iinpinpets
 can-be fabricated by a glasa blower until they
 become available commercially.)
                          IJMJ
  eittUJlOW: M
            II-
 inmc
      LfCt>w
              a- 1
                                 ITS
                           cainui
                                      t S
     Ftfur* 1t-l. 'imrtclrt trtritt
  2.1 J  Glass Wool Stopcock Grease.
Drying Tube, Valve, Pump. Barometer, and
Vacuum Gauge and Rotarneter. Suns as in
Method 6, Sections 2.L3. 2.1X, 2.1.6. 2.1.7.
2.1.8. 2.1.11. and 2.1.12, respectively.
      Section  No.   3.15.10
      Date   July 1,   1986
      Page   5
  2.1.4  Rate Meter. Rotaraeter. or
 equivalent, accurate to within 2 percent at the
 selected flow rate between 400 and 500 cc/
 min. For rotameters. a range of 0 to 1 liter/
 mm it recommended.
  2.1.5  Volume Meter. Dry gas meter
 capable of measuring the cample volume,
 under the sampling conditions of 400 to 500
 cc/min for 60 minutes within an accuracy of 2
 percent
  2.1.6  Filter-To remove NO, from ambient
 air. prepared by adding 20 g of a 5-angstrom
 molecular sieve to a cylindrical tube. e.g.. a
 polyethylene drying tube.
  £l.7  Polyethylene Bottles, l-liter. for
 sample recovery.
  2.1.8  Funnel and Stirring Rods. For sample
 recovery.
  i2  Sample Preparation and Analysis.

  2.2.1  Hot Plate. Stirring type with 50- by
10-mm Teflon-coated stirring ban.
  2^.2  Beakers. 400-. 600-, and 1000-ml
capacities.
  2.2.3  Filtering Flask. 500-ml capacity with
side arm.
  2J.4  Buchner Funnel 75-mm ID, with  .
apout equipped with a 13-mm ID by SO-mm
long piece of Teflon tubing to minimize
possibility of aspirating sample solution
during filtration.
  2.2.S  Filter Paper. Whatman GF/C, 7.0-cm
diameter.
  2.2.6  Stirring Rods.
  2.2.7  Volumetric Flasks. 100-. 200- or 250-,
500-, and 1000-ml capacity.
  2.2.8  Watch Classes. To cover 600- and
1,000-ml beakers.
  2.2.9  Graduated Cylinders. 50- and 250-ml
capacities.
  Z2.10  Pipettes. Class A
  2.2.11  pH Meter. To measure pH from 0.5
to 12.0
  2.2.12  Burette. 50-ml with a micrometer
type stopcock. (The stopcock is Catalogue
No. 8225-1-05. Ace Glass. Inc.. Post Office
Box 096. Louisville, Kentucky 50201.) Place a
glass wool plug in bottom of burette. Cut off
burette at a height of 43 cm from the top of
plug, and have a glass blower attach a glass
funnel to top of burette such that the
diameter of the burette remains essentially
unchanged. Other means of attaching the
funnel are acceptable.
  2.2.13  Glass Funnel. 75-mm ID at the top.
  2.2.14  Spectrophotometer. Capable of
measuring absorbance at 540 nm. One-cm
cells are adequate.
  2.2.15  Metal Thermometers. Bimetallic
thermometers, range 0 to 150 'C.
  2^.16  Culture Tubes. 20-by 150-mm.
Kimax No. 45048.
  2.2.17  Parafilm "M." Obtained from
American Can Company, Greenwich.
Connecticut 00330.
  2.2.18  COi Measurement Equipment
Same es in Method 3.
  3. Reagents.
  Unless otherwise indicated, all reagents
should conform to the specifications
established by the Committee on Analytical
Reagents of the American Chemical Society,
where such specifications are available;
otherwise, use the best available grade.

-------
    3.1   Sampling.
    3.1.1  Water. Deionired distilled to
  conform to ASTM specification D 1193-74,
  Type 3 (incorporated by reference—see
  J 60.17).
    3.1.2  Potassium Permanganate. 4.0 percent
  (w/w). Sodium Hydroxide, 2.0 percent (w/w).
  Dissolve 40.0 g of KMnO. and 20.0 g of NaOH
  in 940 ml of water.
    3.2   Sample Preparation and Analysis.
    3.2.1  Water. Same as in Section 3.1.1.
    3.2.2  Sulfuric Acid. Concentrated HiSO^
    3.2.3  Oxalic Acid Solution. Dissolve 48 g
  of oxalic acid |(COOH)i-2HiO] in water, and
  dilute to 500 ml. Do not heat the solution.
    3.2.4  Sodium Hydroxide. 0.5 N. Dissolve
  20 g of NaOH in water, and dilute to 1 liter.
    3.2.5 Sodium Hydroxide. 10 N. Dissolve
  40 g of NaOH in water and dilute to 100 ml.
    3.2.6 Ethylenediamine Tetraacetic Acid
  (EDTA) Solution. 6.S Percent. Dissolve 6.5 g of
  EDTA (disodium salt) in water, and dilute to
  100 ml. Solution is best accomplished by
  using a magnetic stirrer.
    3.2.7  Column Rinse Solution. Add 20 ml of
  6.5 percent EDTA solution to 960 ml of water,
  and adjust the pH to 11.7 to 12.0 with 0.5 N
  NaOH.
    3.2.8  Hydrochloric Acid (HCI), 2 N. Add
  66 ml of concentrated HCI to a 500-ml
  volumetric flask containing water, dilute to
  volume, and mix well. Store in a glass-
  stoppered  bottle.
    3.2.9  Sulfanilamide Solution. Add 20 g of
  sulfanilamide (melting point 165  to 167 *C) to
  700 ml of water. Add, with mixing. 50 ml
  concentrated phosphoric acid (85 percent).
  and dilute to 1000 ml. This solution is stable
  for at  least 1 month, if refrigerated.
    3.2.10 N-(l-Naphthyl)-Ethylenediamine
  Dihydrochloride (NEDA) Solution. Dissolve
  0.5 g of NEDA in 500 ml of water. An aqueous
  solution should have one absorption  peak at
  320 nm over the range of 260 to 400 nm.

  NEDA, showing more than one absorption
  peak over  this range, is impure and should
  not be used. This solution is stable for at
  least 1 month if protected from light and
  refrigerated.
    3.2.11 Cadmium. Obtained from Matheson
  Coleman and BelL 2909 Highland Avenue.
  Norwood.  Ohio 45212. as EM Laboratories
  Catalogue  No. 2001. Prepare by rinsing in 2 N  .
  HCI for 5 minutes until the color is silver-
  grey. Then rinse the cadmium with water
  until the rinsings are neutral when tested
  with pH paper. CAUTION: Hi is liberated
  during preparation. Prepare in an exhaust
  hood away from any flame.
    3.2.12 NaNOi Standard Solution. Nominal
  Concentration, 100 n g NOr-/ml. Desiccate
  NaNOi overnight. Accurately weigh 1.4 to 1.6
  g of NaNOi (assay of 97 percent NaNOi or
  greater), dissolve in water, and dilute to 1
  liter. Calculate the exact NOi- concentration
  from the following relationship:

                            purity, %           48.01
Mg NO^/ml-g of NaNO,X   	  XIO'X  —
    Section  No.   3.15.10
    Date  July  1,   1986
    Page  6

  This solution is stable for at least 6 months
  under laboratory conditions.
    3.2.13  KNCs Standard Solution. Dry KNOs
  at 110 *C for 2 hours, and cool In • desiccator.

 Accurately weigh 9. to 10 g of KNCb to within '
 0.1 mg, dissolve in water, and dilute to l liter.
 Calculate the exact NO,- concentration from
 the following relationship:
   NOr-/ml-8 of KNO.X10'
            x •               101.10
This solution is stable for 2 months without
preservative under laboratory conditions.
  3.2.14  Spiking Solution. Pipette 7 ml of the
KNOj standard into a 100-ml volumetric
flask, and dilute to volume.
  3.2.15  Blank Solution. Dissolve 2.4 g of
KMn04 and 1.2 g of NaOH in 96 ml of water.
Alternatively, dilute 60 ml of KMnO4/NaOH
solution to 100 ml.
  3.2.16  Quality Assurance Audit Samples.
Same as in Method 7, Section 34.9. When
requesting audit samples, specify that they be
In the appropriate concentration range for
Method 7C.
  4. Procedure.
  4.1  Sampling.
  4.1.1  Preparation of Collection Train. Add
200 ml of KMnOJNaOH solution (3.1.2) to
each of three impingers, and assemble the
train as shown in Figure 7C-1. Adjust probe
heater to a temperature sufficient to prevent
water condensation.
  4.1.Z  Leak-Check Procedure. A leak-check
prior to the sampling run should be carried
out: a leak-check after the sampling run is
mandatory. Carry out the leak-check(s)
according to Method 6, Section 4.1.2.
  4.1.3  Check of Rotameter Calibration
Accuracy (Optional). Disconnect the probe
from the first impinger. and connect the filter
(2.1.6). Start the pump, and adjust the
rotameter to read  between 400 and 500 cc/
min. After the  flow rate has stabilized, start
measuring  the volume sampled, as recorded
by the dry gas meter (DCM), and the
sampling time. Collect enough volume to
measure accurately the flow rate, and
calculate the flow rate. This average flow
rate must be less than 500 cc/min for the
sample to be valid: therefore, it is
recommended that the flow rate be checked
as above prior to each test
  4.1.4  Sample Collection. Record the initial
DCM reading and barometric pressure.
Determine the sampling point or points
according to the appropriate regulations, e.g.,
Section 60.46(c) of 40 CFR Part 60. Position
the  tip of the probe at the sampling point.
connect the probe to the first impinger, and
start the pump. Adjust the sample flow to a
value between 400 and 500 cc/min.
CAUTION: HIGHER FLOW RATES WILL
PRODUCE LOW RESULTS. Once adjusted.
maintain a constant flow rate during the
entire sampling run. Sample for 60 minutes.
For relative accuracy (RA) testing of
continuous emission monitors, the minimum
sampling time is 1 hour, simpling 20 minutes
o
o
o

-------
 at each traverse point. [Note.—When the SO,
 concentration is greater than 1200 ppm, the
 sampling time may have to be reduced to 30
 minutes to eliminate plugging of the impinger
 orifice with MnOi. For RA tests with SO,
 greater than 1200 ppm, sample for 30 minutes
 (10 minutes at each point)). Record the DCM
 temperature, and check the flow rate at least
 every S minutes. At the conclusion of each
 run. turn off the pomp, restore probe from the
 stack, and record the final readings. Divide
 the sample volume by the sampling time to
 determine the average (low rate. Conduct a
 leak-check as in Section 4.1.2. If a leak is
 found, void the test run. or uae procedures
 acceptable to the Administrator to adjust the
 sample volume for the leakage.
  4.1.S  COi Measurement. During sampling.  <
 measure the COt content of the slack gas
 near the sampling point using Method 3. The '
 single-point grab sampling procedure is
 adequate, provided the measurements are
 made at least three times—near the start.
 midway, and before the end of a run and the
 average CO, concentration is computed. The
 Orsat or Fyrite analyzer may be used for this
 analysis.
  4-2  Sample Recovery. Disconnect the
 impingers. Pour the contents of the impingers
 into a 1-liter polyethylene bottle using a
 funnel end a sin-ring rod (or other means) to
 prevent ipillags. Complete the quantitative
 transfer by rinsing the impingers and
 connecting tubes with water until the rinsings
 that are clear to light pink, and add the
 rinsings to the bottle. Mix toe sample, and
 mark the solution level. Seal and identify the
 sample container.
  4.3 Sample Preparation for Analysis.
 Prepare a cadmium reduction column as
 follows: Fill the burette (£2.12) with water.
 Add freshly prepared cadmium slowly with
 lapping until no further Milling occur*. The
 height of the cadmium column should be 39
 cm. When not in use. store the column under
 rinse solution (3.2.7). (Note.—The column
 should not contain any bands of cadmium
 Tines. This may occur if regenerated column
 is used and will greatly reduce the column
 lifetime.)
  Note the level of liquid in the sample
 container, end determine whether any sample
 was lost during shipment If a noticeable
 amount of leakage has occurred, the volume
 lost can be determined from the difference
 between initial end final solution levels, and
 this value can then be used to correct the
 analytical result. Quantitatively transfer the   ,
contents to a 1-liter volumetric flask, and
 dilute to volume.
  Take a 100-ml aliquot of the sample and
blank (unexposed KMnO./NaOH) solutions,
 and transfer to 400-m! beakers containing
magnetic storing bars. Using e pH meter, add
concentrated H.SO. with stirring until a pH
of 0.7 is obtained. Allow the solutions to
stand for 15 mintnes. Cover the beakers  with
watch glasses, and bring the temperature of
the solutions to 50 *C. Keep the temperature
below 60 *C Dissolve 4.6 g of oxalic add m a
minimum volume of water, approximately 50
ml, sit room temperature. Do not heat the
solution. Add this solution slowly, in
increments, until the KMnO. solution
  Section  No.  3.15.10
  Date  July  1,   1986
  Page  7

   becomes colorless. II the color is not
   completely removed, prepare some more of
   the above oxalic acid solution, and add until
   a colorless solution it obtained. Add an
   excess of oxalic acid by dissolving 1.6 f? cf
   oxalic acid in 50 ml of water, and add 6 ml of
   this solution to the colorieis solution. II
   suspended matter is present, add
   concentrated H»SO« until a dear solution is
   obtained.

   Allow the samples to cool to near room
  temorrolure. being sure thtt »h* sampies «re
  still dear. Adjust the pH to 11.7 to 12-0 with
  10 N NsOH Quantitatively transfer the
  mixture to • Buchner funnel containing CF/C
  filter paper, and filter the precipitate. Filter
  the mixture into a 500-m) tillering flask. Wash
  the solid material four times with water.
  When filtration is complete, wash the Teflon
  tubing, quantitatively transfer the filtrate to a
  500-ml volumetric flask, and dilute to volume.
  The samples are now ready for cadmium
  reduction. Pipette a SO-ml  aliquot of the
  sample into a ISO-mi beaker, and add e
  magnetic stirring bar. Pipetie in 1.0 ml of 6.5
  percent EDTA solution, and mix.
   Determine the correct stopcock telling to
  establish a flow rate of 7 to B ml/rein of
  column rinse solution through the cadmium
  reduction  column. Use • 50-ml graduated
  cylinder to collect and measure the solution
.  volume. Alter the last of the nnse solution
  has passed from the funnel into the burette.
  but before air entrapment can occur, start
  adding the sample, and collect it in a 250-m!
  graduated cylinder. Complete the
  quantitative transfer of the sample to the
  column as the sample passes through the
  column. After the  last of'the sample has
  passed from the funnel into the burette, start
  adding GO  ml of column rinse solution, and
  collect the rinse solution until the solution
  just disappears from the funnel.
  Quantitatively transfer the sample to a200-ml
  volumetric flask [250-ml may be required),
  and dilute to volume. The  samples are now
  ready for NOr-4- analysis. (Note.— Both the
  sample and blank should go through this
  procedure. Additionally, two spiked samples
  should be  run with every group of samples
  passed through the column. To do this.
  prepare two additional 50-ml aliquots of the
  sample suspected to have  the highest NOj-
  concentrstion,  and add 1 ml of the spiking
  solution to these aliquots.  If the spike
  recovery or column efficiency (see 6.2.1) is
  below 85 percent,  prepare a new column, and
  repeat the cadmium reduction).
   4.4  Sample Analysis. Pipette 10 ml of
  sample into a culture tube. (Note.—Some test
  tubes give a high blank NO?-value but
  culture tubes do not.) Pipette in 10 ml of
  sulfanilamide solution and 1.4 ml of KEDA
  solution. Cover the culture tube with
  parafilm. and mix the solution. Prepare a
  blank in the same manner using the sample
  from treatment of the unexpo*ed KMnCW
  NaOH solution (3.1.2). Also, prepare a
  calibration standnrd to check the slope of (he
  calibration curve. After a 10-minute color
  development interval, measure the
 absorbance at 540 nm against water. Rend UK
 NOr-/ml from the calibration curve. If the

-------
 absoruance i« freater than that of the highest
 calibration standard, pipette less than 10 ml
 of (ample and enouph water to make the total
 •ample volume 10 ml. and repeat the
 analysis. Determine the No> concentration
 using the calibration curve obtained in
 Section 5.3.
  4.5 Audit Analysis. This is the same as in
 Method?. Section 4.4.
  5. Calibration.
  5.1 Dry Cat Metering System (DCM).
  5.1.1 Initial Calibration. Same as in Method
 6. Section 5.1.1. For detailed instructions on
 carrying out this calibration, it is suggested
 that Section 3.5.2 of Citation 4 in  the
 bibiography be consulted.
  5.1.2  Post-Test Calibration Check. Same
 as In Method 6, Section 5.1.2.
  5.2  Thermometers for DCM and
 Barometer. Same as in Method 6. Sections 5.2
 •nd 5.4. respectively.
  5.3  Calibration Curve for
 Spectrophotomeicr. Dilute 5.0 ml of the
 NaNOi standard solution to 200 ml with
 water. This solution nominally contains 25 fig
 NCWml. Use this solution to prepare
 calibration standards to cover the range of
 0.25 to 3.00 fig N0r-/ml. Prepare a minimum
 of three standards each for the linear and
 slightly nonlinear (described below) range of
 the curve. Use pipettes for all additions.
  Run standards and a water blank as
 instructed in Section 4.4. Plot the net
 absorbance vs fig NOr-/ml. Draw a smooth
 curve through the points. The curve should be
 linear up to an absorbance of approximately
 1.2  with a slope of approximately 0.53
 absorbance units/fig NOt-/ml. The curve
 should pass through the  origin. The curve is
 slightly nonlinear from an absorbance of 1.2
 to 1.6.
  6. Calculations.
  Carry out calculations, retaining at least
 one extra decimal figure beyond that of the
 acquired data. Round off figures after final
 calculation.
  6.1 Sample volume, dry basis, corrected to
 standard conditions.
        Section  No.  3.15.10
        Date  July  1,   1986
        Page  8

    67  Total fig NO, Per Sample.
    6.Z1  Efficiency of Cadmium Reduction
  Column. Calculate this value es follows:
                                                                                                                                   o
E.«
        (* -
      s x 1.0 x
269.6 (x!-  y)
       s
                  (Eq.  7C-2)
        Where:
        E—Column efficiency, unitless.
        x—Analysis of spiked sample, fig NCWml.
        y» Analysis of unspiked sample, fig NO?-/
            ml.
        200«»Final volume of sample and  blank after
            passing through the column, ml
          s-Concentration of spiking solution, ftg
              NO,/ml.
          1.0—Volume of spiking solution added, ml.
         ' 4fi.01«tfig NO~/fimole.
          62.01«»fig NOj-/fimole.
            6.2.2  Total fig NO,.

     (S-B)        500    1000     (2X101 (S-B)
m-	  X200X —  X 	 •= 	
       E           50     100          E

                   "(Eq. 7C-3)

         Where:               ,
         m«=Musi of NO,, as NOi. in sample, fig.
         S-Analysis of sample, fig NOr-/ml.
         B-Analysis of blank, fig NO^/ml.
         500—Total volume of prepared sample, ml.
         50-Aliquot of prepared sample processed
            through cadmium column, ml
         100 - Aliquot of KMnOi/NaOH solution, ml.
         1000-Total volume of KMnOWNaOH
            solution ml.
           6.3 Sample Concentration.
                      -K.XY
                                L=I     fEq. 70-1)
                                                                                                C-K,
                                                                                                         m
Where:
V.i^-Dry gas volume measured by the dry
    pas meter, corrected to standard
    conditions, dscm.
Vm " Dry gas volume «s measured by the dry
    gas meter, don.
Y — Dry gas meter calibration factor.
X— Correction f actor f or CO« collection.
                     100
       Where:
       ^Concentration of NO, as NO:, dry basis.
           mg/dscm.
            "  IOO«1ECOi(v/v)

Ptar-Barometric pressure, mm fig.
PM-Standard absolute pressure, 7CO mm Hg.
Tm » Avers?* dry jras meter absolnte
    temperature, "K.
TMB Standard absolute temperature. 233 *K.
                                               'I
         6.4  Conversion Factors.
       1.0 pptn NO -1.247 mg NO/m* at STP.
       1.0 ppm NOj-1.912 mg NOi/m'at STP.
       lft1-2.832X10-1m3.
         7. Quality Control.
         Quality control procedures are specified in
       Sections 4.1.3 (flow rate accuracy); 4.3
       (cadmium column efficiency): 4.4 (calibration
       curve accuracy); and 4.S (audit analysis
       accuracy).
         8. Bibliovraphv.         ,
         1. Marge'son. ).H.. W.J. Mitchell. J.C. Suygs.
       and M.R. Mldgett. Integrated Samplins and
       Analysts Methods for Determining NO,
       Emissions at Electric Utility Plants. U.S.
       Environmental Protection Agency. Research
       Triangle Park. N.C. Journal of the Air
       Pollution Control Association. J21210-1215.
       1982.
                        O
                        O

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                                                                            Section  No.   3.15.10
                                                                            Date  April  16,  1986
                                                                            Page  9
  2. Memorandum and attachment from J.H.
Margeson. Source Branch. Quality Assurance
Division. Environmental Monitoring Systems
Laboratory, to The Record. EPA. March 30.
1983. N'H> Interference in Methods "C and 70.
  3. Margeson. ).H, f.C. Suggs, and M.R.
Midgett Reduction of Nitrate to Nitrite with
Cadmium. Anal. Chem. 52:1955-5'. 1960.
  4. Quality Assurance Handbook for Air
Pollution Measurement Systems. Volume
III—Stationary Source Specific Methods.
August 1977. U.S. Environmental Protection

Ajzency. Research Triangle Park. N.C
Publication No. EPA-600/4-77-027b. August
1977.
  5. Margeson. J.H.. et al. An Integrated
Method for Determining NO, Emissions at
Nitric Acid Plants. Manuscript submitted to
Analytical Chemistry. April 1884.

-------
                                             Section No. 3.15.11
                                             Date April 16, 1986
                                             Page 1
11.0  REFERENCES
      12. Gjerde,  D. T., J. S. Fritz, and G. Schmuckler.   Anion
          Chromatography  with Low-Conductivity Eluents.  Journal
          of Chromatography.  186, 509, 1979.
o
      1.  Federal  Register,  Volume 49, No. 189,  September  27,
          1984.   Method  7D - Determination  of  Nitrogen  Oxide
          Emissions  From  Stationary  Sources,  Alkaline-Perman-
          ganate/Ion Chromatographic Method.

      2.  Margeson,  J.  H.,  J. E. Knoll, M. R. Midgett, , G.  B.
          Oldaker III,  K.  R.  Loder,  P.  M.  Grohse, and W. F.
          Gutknecht.    Integrated  Method  for  Determining  NO
          Emissions at Nitric Acid Plants.  Analytical Chemistryf
          5j6, 2607, 1984.

      3.  Small,  H. T., S. Stevens, and W. C. Bauman.  Novel Ion
          Exchange Chromatographic  Method  Using  Conductimetric
          Determination.  Analytical Chemistry, 47, 11:801, 1975.

      4.  Johnson,   E.   L.  and  R.  Stevenson.   Basic  Liquid
          Chromatography.  Varian Associates, Inc., 1978.

      5.  Yost,  R. W., L. S. Ettre, and R. D. Conlon,  Practical
          Liquid Chromatography, An  Introduction.  Perkin-Elmer,
          1980.

      6.  Smith,  F.  C.,  Jr., and R. C. Chang.  The Practice of   [)
          Ion Chromatography.   John Wiley and  Sons,  Inc.,   New   V_x
          York, 1983.

      7.  Stevens,  T.  S.  and M.  A.  Langhorst.  Agglomerated
          Pellicular     Anion-Exchange     Columns    for    Ion
          Chromatography.  Analytical Chemistry, 54, 6:950, 1982.

      8.  Stevens,  T.  S.,  G.  L.  Jewett,  and R. A. Bredeweg.
          Packed   Hollow  Fiber  Suppressors  for  Ion   Chroma-
          tography.  Analytical Chemistry, 54, 7:1206, 1982.

      9.  Mulik,  J.  D.,  and  E.  Sawicki.  Ion Chromatography.
          Environmental Science and Technology, 13, 7:804, 1979.

      10. Sevens, T. S., J. C. Davis, and H. Small. Hollow'Fiber
          Ion   Exchange   Suppressor   for  Ion  Chromatography.
          Analytical Chemistry, 53, 9:1488, 1981.

      11. Stevens, T.  S.  Packed  Fibers  and  New Columns Speed,
          Simplify  Ion  Chromatography.  Industrial Research and
          Development, September 1983.
                                                                    O

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12.0  DATA FORMS
                                            Section No.  3.15.12
                                            Date October 23,  1985
                                            Page 1
    Blank data forms  are provided on the following pages  for the
convenience  of  the  Handbook  user.   Each  blank  form  has the
customary descriptive title centered  at  the  top  of  the page.
However, the section-page documentation  in  the  top  right-hand
corner of each page  of  other  sections has been replaced with a
number in the lower right-hand corner  that  will enable the user
to  identify  and refer to a similar filled-in  form  in  a  text
section.  For example, Form M7D-1.1  indicates  that  the  form is
Figure 1.1 in Section 3.15.1  of  the  Method 7D section.   Future
revisions of these forms, if  any,  can  be  documented by 1.2A,
1.2B, etc.  Twelve of the blank forms listed  below  are included
in this section.  Four are in the Method Highlights subsection as
shown by the MH following the form number.
Form

1.1

2.2

2.4A and 2.4B


2.5 (MH)

3.1 (MH)

4.1

4.2

4.3

4.4 (MH)

5.1


5.3


5..4 (MH)

6.1A and 6.IB


8.1
Title

Procurement Log

Wet Test Meter Calibration Log

Dry Gas Meter Calibration Data Form (English
and Metric Units)

Pretest Sampling Checks

Pretest Preparations

Field Sampling Data Form for NO

Sample Label

Sample Recovery and Integrity Data

On-Site Measurements

Analytical Data Form for Analyses of
Calibration Standards

NO  Laboratory Data Form for Analyses of
Field Samples

Posttest Operations

Nitrogen Oxide Calculation Form (English and
Metric Units)

Method 7D Checklist to be Used by Auditors

-------
                                       Section No.  3.15.11
                                       Date A
                                       Page 2
Date April 16, 1986  S~*\
13. Margeson, J. H., W. J.  Mitchell,  J.  C. Suggs,  and M. R.
    Midgett.  Integrated Sampling and  Analysis Methods for
    Determining  NO   Emissions at Electric Utility Plants.
    Journal of the sir  Pollution  Control Association, 32,
    1210, 1982.

14. Eubanks,  D.  R.,  and  J.  R.  Stillian.  Care  of Ion
    Chromatography   Columns.   Liquid  Chromatography,  2_,
    2:74, 1984.

15. Hamil,  Henry F., et. al.  The Collaborative  Study  of
    EPA  Methods  5,  6,  and  7 in Fossil Fuel Fired Steam
    Generators.  Final Report, EPA-650/4-74-013, May 1974.

16. Hamil, H. F., and R. E. Thomas.  Collaborative Study of
    Method   for   the  Determination  of  Nitrogen   Oxide
    Emissions from Stationary Sources (Nitric Acid Plants).
    EPA-650/4-074-028, May 1974.

17. Hamil, Henry F.  Laboratory  and  Field  Evaluations of
    EPA Methods  2,  6,  and 7.  Final Report, EPA Contract
    No.  68-02-0626,   Southwest  Research  Institute,  San
    Antonio, Texas, October 1973.
                                                             o
                                                             o

-------
           PROCUREMENT LOG
Purchase
 order
 number
                               Quality Aoauronoo  Handbook M7D 1.1

-------
                                    WET TEST METER CALIBRATION  LOG
 wet teat meter serial number
          Date
 Range of wet test meter flow  rate
 Volume of test flask Vs = 	
   Satisfactory leak check? 	
   Ambient temperature of equilibrate liquid in wet test meter and reservoir
Test
number
1
2
3
Manometer
reading, a
mm l^o



Final
volume (Vf),
L



Initial
volume (Vj) ,
L



Total
volume, (Vm)
L



Flask
volume (V ) ,
L



Percent
error, c
%



 aMust be less than 10  mm (0.4 in.) H2O.
 Calculations:
     " vf -
 c%  error = 100 (Vm - VS)/VQ =
(+1%).
                               Signature of  calibration person
o
    o
                                                                Quality Assurance  Handbook M7D-2.2
o

-------
                            DRY GAS  METER  CALIBRATION
                                                           FORM (ENGLISH UNITS)
      Date
                    Calibrated by
                                           Meter box number
           Wet test meter number
      Barometer pressure, P
                          ffl
                                       in. Hg   Dry gas meter  temperature correction factor
Wet test
meter
pressure
drop

-------
Date
                   DRY GAS  METER CALIBRATION DATA FORM (METRIC UNITS)
               Calibrated by  	  Meter' box number 	'   Wet test meter number
Barometer pressure,  P  =
                                  in.  Hg   Dry gas meter temperature correction factor
Wet test
meter
pressure
drop
(IV'a
mm H20



Rota-
meter
setting
(Rs),
cc/rain



Wet test
meter gas
volume
< V 'b
L



Dry test meter
gas volume
(Vd),b L
Initial



Final



Wet test
meter
gas temp
,
°C



Inlet
gas
temp
'V
°C



Dry test meter
Outlet
gas temp
o
°C



Average
gas temp
°C



Time
of run
(9),d
min



Average
ratio



i



  D  expressed as  negative number.
  Volume passing through meter.  Dry gas volume is minimum for  at  least five revolutions of the meter.
c The average of td  and td  if using two thermometers;  the actual reading if using one thermometer.
d                 i       O                                   .   .
  The time it takes to complete the calibration run.
6 With Y defined as the average ratio of volumes for  the wet test  and the dry test meters, Yi = Y +0.02 Y for
  calibration and Y^^ = Y +0.05 Y for the posttest checks;  thus,
     Vw (td + 273°C)  [Pm + (Dm/13.6)]
   Vd (tw
                  273°C)  (P)
                          m
                                 (Eq. 1)
                                                   and
Y =
(Eq.  2)
  With Y  defined  as the average ratio of volumetric measurement by wet test meter to rotameter.
  Tolerance Yr = 1 +0.05 for calibration and Y +_0.1  for posttest checks.
Vw (td + 273°C)
                           (Dm/13.6)
          (tw + 273°c>
                                 (Eq . 3 )
                                                  and
                                                       o
                                   (Eq. 4)
                                                                    Quality  Assurance  Handbook M7D-2.4B
                                                                                                    o

-------
Plant name
Location 	
Operator
                           FIELD  SAMPLING DATA  FORM FOR NO
                     City
                     Date
                     Sample no.
Probe length/material
Meter box no.
Sampling point location(s)
Rotameter setting 	
Initial leak check? 	
C00 concentration  (1)
                                (2)
                     Probe setting 	
                     Meter factor (Y) 	
                     Bar press mm (in.) Hg
                     Rotameter check? 	
                     Final leak check? 	
                        (3) 	
avg
Sampling
time,
min









-




Total
Clock
time
2H h















Dry gas
meter
readings
L (ft3)














Total
Sample flow
rate setting,
cc/min (ft^/min)















Sample volume
metered,_(V )
L (ft3) m






•







V
m
avg
Percent
deviation,
%














Avg
dev
Dry gas
meter temp
°C (°F)













•
Avg
^Percent deviation =
V   —  V  ave
 m      m  B x 100  (must be less  than 10 percent).
                        V  avg
                                     Quality Assurance Handbook M7D-4.1

-------
SAMPLE LABEL
                                        o
Plant
Site " v '
Date
Front rinse
Back rinse L
Solution
Volume: Initd
Cleanup by

City
Sample type
Run number
J Front filter 1 J Front solution 1 	 1
Back filter | 	 | Back solution 1 1
Level marked «
Lai Final %
E
0)
kt.




































                                         o
    Quality Assurance Handbook M7D-4.2
                                          O

-------
Plant
                SAMPLE RECOVERY AND INTEGRITY DATA
Sampling location
                        Field Data Checks
Sample recovery personnel 	
Person with direct responsibility for recovered samples
Sample
number
1
2
3
Blank
Sample
identification
number




Date
of
recovery




Liquid
level
marked




Stored
in locked
container




Remarks
Signature of field sample trustee
                      Laboratory Data Checks
Lab person with direct responsibility for recovered samples
Date recovered samples received 	
Analyst
Sample
number
1
2
3
Blank
Sample
identification
number




Date
of
analysis




Liquid
level
marked




Stored
in locked
container
•



Remarks
Signature of lab sample trustee
                               Quality Assurance Handbook M7D-4.3
                                             O'7-
                 7-

-------
            ANALYTICAL DATA FORM FOR ANALYSES  OF CALIBRATION STANDARDS
 Plant

 Date
                     Location

                     Analyst
                                                                               o
Standard
identifier
Std 1
Std 2
Std 3
Std 4
Standard
concentration (x)
(pg/inl N03 )




Instrument response (y)
peak height or area count
nun
1




2




3




Avg




Predicted
standard
concentration (P)
(Vg/nl N03 )




Deviation
.(*)."




Equation for Linear Calibration Curve, Average Response as  a Function of Standard
Concentration
    y = mx +  b =  (
    ) x
 where:
    y =  instrument response (mm or area count) =
    m = calibration curve slope
          mm or area count
            yg NO ~/ml
                                                                                O
    x = standard concentration (yg NCL /nl) =
    b = I = intercept term (mm or area count) = 	

Predicted Standard Concentration (P)

    P ( C NO ~/ 1) - AveraSe Instrument Response (y)  -  Intercept (I)
            ^              Calibration Curve Slope (B)
    P (for first standard)
                                         V g NO ~/ml
Deviation

    Deviation  (%) .
fag
    Deviation
    (of first set    ,
    of standards) =  -
                                  - x (yg NO^/ml)
                             x (yg N03"/mL)
                      x 100*
                                       Quality Assurance Handbook  M7D-I
                                            (/*"

-------
           N0v  LABORATORY DATA FORM FOR ANALYSES  OF FIELD SAMPLES
             X
  Date samples received

  Plant
  Location
  Calibration curve slope (m)
                 Date samples analyzed
                           Run number(s)
                  Analyst
                    Intercept term  (I)
Field
sample
number



Field
Blank
Analysis
number
1st
2nd
1st
2nd
1st
2nd
1st
2nd
Instrument
response (y)
(mm or area counts)




Concentration of
analysis samgle
(ug/ml NO. )




Average
Concentration of
analysis samgle
( Vg/ml N0_ )
S =
S =
S =
B =
Deviation
(*)




Concentration of
Analysis Sample
(Vg N03"/ml)

Concentration
(of first sample)
  Instrument Response (y) - Intercept  (I)

       Calibration Curve Slope (m)
Deviation
Deviation
(of first
standard set)
   Sample Concentration - Average Concentration
S5             • '	-~	     '-          ' ' —        X
            Average Concentration
                      x 100* =
                                      Quality Assurance Handbook M7D-5.3

-------
             NITROGEN OXIDE CALCULATION FORM (ENGLISH UNITS)
                          Sample Volume
                                                                   o
Vm =_
Pbar =
                    dcf, Y =
                    n. Hg, T
   R
Vm(std) = 17-64
                    \bar =
                         m
dscf
Equation 6-1
                    Total yg N02 Per Sample
S =	vg/ml, B =	yg/ml
m =  3710 (S -B) =
                                      of N0
             Equation 6-2
                          Sample Concentration
C = 2.205 x 10
              -9    m
                                         x 10~5 Ib/dscf
                                                                   O
                  V
                   m(std)
                                                       Equation 6-3
                      Sample Concentration in ppm
ppm NO2 = 8.375 x 10  C =
                                      ppm
             Equation 6-4
                                 Quality Assurance Handbook M7D-6.1A
                                                                  O

-------
vm = o.o
            NITROGEN OXIDE CALCULATION FORM (METRIC UNITS)



                           Sample Volume
        m3,  Y =
 bar ~	
mm Hg,  Tm =
                                          K
Vm(std) = °-3858 x y
            = 0.0	dscm     Equation 6-1
                         m
                      Total vg N02 Per Sample
S =	yg/ml,   B = 	
m = 3710 (S - B) =
                  vg/ral
              	 vg of N02
Equation 6-2
C = 10
      -3     m
           'm(std)
                       Sample Concentration
   	mg NO2/dscm
Equation 6-3
                   Sample Concentration in ppm
ppm N02 = 0.5228 C =	ppm
                    NO,
Equation 6-4
                                   Quality Assurance Handbook M7D-6.1B

-------
METHOD 7D CHECKLIST  TO BE USED BY AUDITORS
                                                            o
Yes
No
Comment
OPERATION
            PRESAMPLING PREPARATION

  1.  Knowledge of process conditions

  2.  Calibration of pertinent equipment,  in particular,
      the dry gas meter and rotameter, prior to each  field
      test
           ON-SITE MEASUREMENTS

  3.  Leak-testing of sampling train  after sample run

  4.  Preparation of absorbing solution and its addition
      to impingers

  5.  Constant sampling at less than  500 cc/min

  6.  Measurement of CO- content

  7.  Recording of pertinent process  conditions during
      sample collection

  8.  Maintaining the probe at a given temperature
                                                                                  O
             POSTSAHPLINQ

  9.  Control sample analysis - accuracy and precision

 10.  Sample aliquotting techniques

 11.  Ion chromatographic technique

       a.  Preparation of standard nitrate samples
       (pipetting)
       b.  Calibration factor (jf? %  for all standards,
       optional)
       c.  Adequate peak separation

 12.  Audit results (+10X)

       a.  Use of computer program
       b.  Independent check of calculations
               COMMENTS
                    Quality Assurance Handbook M7D-J

-------
                                                                 Section No.  3.16
                                                                 Date June 30,  1988
                                                                 Page 1
                                    Section 3.16 '•
                METHOD 18 — MEASUREMENT OF GASEOUS ORGANIC COMPOUND
                          EMISSIONS BY GAS CHROMATOGRAPHY
                                      OUTLINE
     Section

SUMMARY
METHOD HIGHLIGHTS
METHOD DESCRIPTION
     1.   PROCUREMENT OF APPARATUS
          AND SUPPLIES
     2.   CALIBRATION OF APPARATUS
     3.   PRESAMPLING OPERATIONS
     4.   ON-SITE MEASUREMENTS
     5.   POSTSAMPLING OPERATIONS
     6.   CALCULATIONS
     7.   MAINTENANCE
     8.   AUDITING PROCEDURE
     9.   RECOMMENDED STANDARDS FOR
          ESTABLISHING TRACEABILITY.
    10.   REFERENCE METHODS
    11.   REFERENCES
    12.   DATA FORMS
Documentation
3.16
3.16
3-16.1
3-16.2
3.16.3
3.16.4
3-16.5
3-16.6
3-16.7
3.16.8
3.16.9
3.16.10
3-16.11
3.16.12
Number
of Pages
3
19
16 ,.-
15
44
/ 33 .=...
39
6
3
8
1
22
5
21

-------
                                                                    Section No. 3.16
                                                                    Date  June 30, 1988
                                                                    Page  2

      To  assist  the Handbook user in applying Section 3-16 to particular  sampling
 and analytical techniques,  the following   table provides a quick cross reference to
                                                                           o
 each  of  the
 approaches.
subsections   dealing  with  each   of  the  sampling  and   analytical
            CROSS REFERENCES TO SUBSECTIONS RELATED TO SAMPLING  APPROACHES


Activity
Procurementof equipment
Saopling
Analytical
Reagents
Calibration
Sanpllng equipment
Presanpling operations
Survey measurements
Survey preparations
Saople collection
Sample analysis
Interpretation of data
Preparation for test:
equipnent
reagents
Packing equipment
On-site Measurements
Sanpling
Postsampling Operations
Prepartion of calibration
standards
Audit sample analysis
Sample analysis
Calculations
Emission calculations
Auditing Procedures
Performance audits
System audits

All
Methods

l.lpl*
1.2p8
1-3P9

2.1pl

3-lpl
3-2pl
3-3P10
3.4pl3
3-4pl9

3.5p21
3.6P30
3-7P32

4.3P2


5-lpl
5-2p22
5-3P22

S.Opi

S.ipl
8.2p5

Flask
Sampling

1.1P3
1.2p8
1-3P9

2.1pl

3-lpl
3-2p8
3-3P11
3.*pl7
3-*pl9

3-5P28
3-6p30
3-7P32

N/A


5-lpl
N/A
N/A

6.1pl

N/A
N/A
Rigid
Container
Sampling

I.lp4
1.2p8
1-3P9

2.1pl

3.1pl
3-2 P9
3-3pl2
3.4pl8
3-4pl9

3-5P28
3-6p30
3-7P32

A.3p2


5-lpi
5-2p22
5-3P22

6.lpi

S.ipft
8.2P5
Direct
Bag
Sampling

l.lpA
1.2p8
1-3P9

2.1pl

3-lpl
3-2p9
3.3P12
3.4P18
3-4pl9

3-5P28
3.6p30
3.7P32

*.3P9


5-lpl
5-2p22
5.2P22

6.1P1

8.1P4
8.2p5
Direct
Interface
Sampling

I.lp6
1.2p8
1-3P9

2.1pl

3-lpl
H/A
»/A
H/A
3-*pl9

3-5P29
3.6P30
3-7P32

4-3P13


5-ipl
5-2p22
5.2P23

6.lpl

8.lp4
8.2p5
Dilution
Interface
Sampling

l.lp?
1.2p8
1-3P9

2.2p9

3-lpl
N/A
N/A
N/A
3-*Pl9

3-5P29
3-6P30
3-7P32

ft.3pl<


5-lpl
5-2P22
5-2p25

6.1pl

8. IPS
8.2p5
Adsorption
Tube
Saapling

1.1P3
1.2p8
1-3P9

2.1pl

3-lpl
3-2pio
3-3pl2
3-*pl9
3.*Pl9

3-5P28
3-6P30
3-7P32

4.3P17


5-lpl2
5-2p22
5-2p26

6.2p2

8-1P5
8.2P5
                                                                                           O
• "l.lpl" - Means that the procurement  of the  sampling equipment is dicussed in Section 3.16.1.1
  beginning on page  1 of Section 3.16.1.
                                                                                          O

-------
                                                                 Section No.  3.16
                                                                 Date June 30,  1988
                                                                 Page 3
                                SUMMARY
     Method  18  is  a generic method for measuring gaseous organic compounds.  The
method is based on separating the major gaseous organic components of a gas mixture
with  a  gas chromatograph (GC) and  measuring  the  separated  components  with  a
suitable  detector.   The  gas samples are analyzed immediately as taken  from  the
stack or within a set period of time after being collected in a Tedlar bag or on an
adsorption tube.
     To  identify and quantify,the major components, the retention  times  of  each
separated component are compared' with  those  of  tknown  compounds under identical
conditions.  Therefore,, the analyst must identify approximate concentrations of the
organic emission components beforehand.  With this  information,  the  analyst  can
then prepare or purchase commercially available standard  mixtures to calibrate the
GC under physical conditions  identical to those that will be used for the samples.
The  analyst  must  also  have  some presurvey information concerning interferences
arising from other compounds present and indicating the need for sample dilution to
avoid  detector saturation, gas stream filtration to eliminate particulate  matter,
and prevention of sample loss in moisture condensation in the sampling apparatus.
     This method is  structured  to  analyze  approximately 90 percent of the total
gaseous organics emitted from an industrial source.  It does not include techniques
to identify and measure trace amounts of organic compounds,  such as those found in
building air and fugitive emission sources.
     This method will not determine compounds that 1) are polymeric (high molecular
weight), 2) polymerize  before  analysis,   or  3)   have very low vapor pressures at
stack or instrument conditions.
     The range of this  method is from about 1 part per million (ppm)* to the upper
limit governed by GC detector saturation or column overloading.   The  upper  limit
can  be  extended by diluting the stack gases with an inert gas or by using smaller
gas sampling loops.  The sensitivity limit for a compound is defined as the minimum
detectable concentration of that compound, or the  concentration  that  produces  a
signal-to-noise ratio of three  to  one.    The minimum detectable concentration and
limit  of  quantitation  are determined during the presurvey calibration  for  each
compound.                                                           12
     The method descriptions given herein  are  based  on the method *  promulgated
October 8, 1983 • and  on  corrections  and  additions  published  on  May  30, 1984
(Section 3-16.10).   Revisions  to the method were promulgated February 19t 198? and
these are also described.    Blank  forms  for  recording  data are provided in the
Method Highlights and in Section 3-3.12 for the convenience of Handbook users.

*Note:  Selective  detectors  may  allow  detection and quantitation of far smaller
        concentrations of certain types of gaseous organic compounds.

-------
                                        Section No. 3.16
                                        Date June 30,  1988
                                        Page 4
                                                                                    o
METHOD  HIGHLIGHTS
     Section 3-16 describes procedures and specifications   for  determining gaseous
organic  compounds  from  stationary sources.  A gas sample is extracted  froa  the
stack  at  a  rate proportional to the stack velocity using one of four techniques:
(1) integrated bag sampling, (2) direct interface  sampling,  (3)  dilution interface
sampling,  and  (4) adsorption tube sampling.  For the first  three techniques,   the
sample or diluted sample is introduced directly into the sample   loop  of  the  gas
chromatograph (GC).  The measured sample is then carried  into the GC column with a
carrier  gas where the organic compounds are separated.  The  organic compounds then
are each measured quantitatively by  the  GC detector.  The qualitative analysis is
made  by  comparing  the  retention  times  (from  injection  to detection) of  known
standards  to  the retention times of the sample compounds.   Once sample  cospounds
are  identified,  quantitative  analysis is made by comparing the detector response
for the sample compound to a known quantity of corresponding  standard.  Gas samples
collected  on  adsorption  tubes are desorbed from the  adsorption media  using  a
solvent.  A measured volume  of  the  desorption solution  is  injected into a heated
injection port where the mixture vaporizes and is carried  into the GC column with a
carrier  gas.   The  sample  is  separated into  the  individual   components,   then
qualitatively and quantitatively analyzed in the same manner  as a gas sample.
     Because of the number  of  different  combinations  of sampling, sample prepar-
ation,  calibration procedures,  GC column materials and operating  procedures, and GC
detectors covered under this method,  a  set of tables (appearing at the end of the
Method Highlights section) has been developed to assist  the tester in selecting and
the test observer in approving an  acceptable  sampling  and  analytical technique.
The compounds listed in these tables were selected based on their current status as
either presently regulated  or  being  evaluated  for future  regulations by EPA and
state and local agencies,  "fable  A  lists selected organic compounds for Method 18
and provides the user with: (1) the Chemical Abstracts (CA) name,  any synonyns,  the
chemical  formula,  the  Chemical  Abstracts  Service  (CAS)  number;   (2)  nethod
classification and corresponding  references  for morej.information; and (3) whether
EPA currently has an audit cylinder for this compound.
     For a given compound, the sampling  and  analytical  techniques  described  in
Tables  B,  C,   D  and  E  are classified in Table A (Status  of   Selected  Organic
Compounds for Method 18 Sampling and Analysis  Techniques)  into one of five classes
as follows:
     1.   Reference  (R).   This  is  a method promulgated by EPA as the conpliance
          test method for one or more EPA emission regulations.
     2.   Tentative  (T).   This  is  a method  where EPA method developnent  is
          completed and documented, but the method has not been promulgated.
     3.   Development (D).  This is a method currently under  development by EPA.
     4.   Other  (0).  This is a method developed and documented  by an organization
          other than EPA.
     5.   None  (N).  This is a method that has not been developed or validated but
          should work based on experience with similar situations.
     Table B shows all the sampling techniques  described   in Method 18.  For each
compound, each of the  allowed sampling techniques is rated either: (1) recosaend-
ed, (2) acceptable, (3) theoretical,  (4)  not  recommended,  or   (5) unknown.   The
rating codes for sampling are based on the extent of method validation.  A particu-
lar  sampling technique is rated based on current EPA methodology.  Where EPA  neth-
odology does not exist, methodology provided by organizations other than the EPA is
used for  rating.    As  an example on how to use Table B,  the rating for benzene is
"T"  for direct interface, "R-12" for Tedlar bags,  and "A-9,13" with carbon  disul-
                                                            o

-------
                                                                 Section No. 3.16
                                                                 Date June 30, 1988
                                                                 Page 5

 fide   for  adsorbent tubes.  This .means that for sampling, there is  no  documented
 experience with the direct interface  method,  but  in  theory it could be valid; a
 Tedlar bag is recommended as a sampling technique and Reference 12 provides further
 description; and charcoal tubes using carbon disulfide as the desorption liquid are
 acceptable and References 9 and 13 provide further description.
     Before a final sampling technique is selected,  the source tester will need to
 consider the general strengths and weaknesses of each technique in addition  to the
 guidance  provided  in  Table  B.   The  strengths  and weaknesses for the sampling
 techniques described in*Method 18 are as follows:

 Direct Interface or Dilution Interface
Strengths:
1.
2.
Weaknesses;
1.
2.
             3.
             4.
Tedlar Bag

Strengths:
Weaknesses:
2.
3-

k.
1.
Adsorbent Tubes

Strengths:   1.

             2.
             3.
Can immediately determine if analysis is successful.
Samples  collected  are in a form that approximates  the  form  in
stack  emissions  and  minimizes  the time for degradation through
polymerization, condensation, etc.
No loss or alteration  in compounds due to sampling since a sample
collection media  (bag or adsorbent) is not used.
Method of choice  for steady state sources when duct temperature is
below 100°C and organic concentrations  are  suitable  for  the GC
detector.
GC must be located at the sampling site.
A GC equipped with a flame ionization  detector   (FID)  cannot  be
operated  at a sampling site  if the presence of  the H? flame will
be hazardous.
Cannot sample proportionally or obtain a time integrated sample.
Because results represent only instantaneous  values, they are not
totally indicative of non-steady state processes.
Samples  collected  are  in  a  form that approximates the form in
stack emissions.
Samples may be returned to the laboratory for GC analysis.
Multiple  analyses,  if  necessary,   may  be  performed  on  each
collected sample.
Samples can be collected proportionally.
Unless protected, Tedlar bags  are  awkward and bulky for shipping
back  to  the  laboratory.   Caution  must be taken to prevent bag
leaks.
Stability of compound(s) of interest in Tedlar bags with time must
be known.  (Maximum permissible storage  time(s)  must be known or
determined, and must not be exceeded.)
Polar compounds  generally  should  not  be  collected  due to bag
adsorption.  There are some exceptions (i.e., ethylene oxide).
Samples  may  not  be  collected when  the  concentration  of  any
component present is within explosive limits.
    Samples collected are compact and easy to return to the laboratory
    for analysis.
    Samples may be returned to the laboratory for GC analysis.
    Sample storage time generally can be extended to a week by  keeping

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                                                                 Section No. 3«l6
                                                                 Date June 30, 1988 ^^^
                                                                 Page 6            i)

                 samples  at  0°C.   However,  the migration of the collected  com-
                 pound(s) through the  charcoal  to  the  backup  portion  may be a
                 problem.
Weaknesses:  1.  Quantitative recovery percentage of each organic compound from the
                 adsorbent material must be known.
             2.  Breakthrough sample gas volume for organic compounds as present in
                 the source matrix must be known for the adsorbent material.
             3.  Any  effect  of  moisture  (in  the  stack  gas) on the  adsorbent
                 material collection  capacity  must  be  known.   Moisture  in the
                 sample  above  2 to 3 percent may severely reduce  the  adsorptive
                 capacity.
             4.  Generally,  samples  can  be  collected  conveniently  only  at  a
                 constant rate.
             5.  Samples must be returned to the lab for analysis.
     Table  C lists the recommended GC detectors commonly used with Method 18.  For
each compound, each GC detector is rated either: R - recommended,  A  - acceptable,
T -  theoretical, N - not recommended, or U - unknown.  A particular GC detector is
rated  based  on current EPA methodology.  Where EPA methodology  does  not  exist,
methodology provided by organizations other than the EPA is used for rating.  As an
example  on how to use Table C, the rating for benzene  is  "R-4,12"  for  a  flame
ionization detector (FID), "N" for an electron capture detector (ECD), "T-38" for a
photoionization detector (PID), and "N"  for  an electrolytic conductivity detector
(ELCD).  This means an FID  is  recommended as the GC detector and References 4 and
12 provide further description, an ECD and  an  ELCD are not recommended, and there ^-^
is no documented experience with a PID for benzene,  but  its  use is theoretically f   )
possible based on the ionization potential found in Reference 38.                   V	'
     Table D presents information on packed columns suitable for GC analysis of the
selected compounds.   Items  covered  include  column  type  and conditions, Kovats
Retention Indices (KRI's), if available, and associated literature references.  The
recommended  column  appears  first, the others are acceptable.  Specifically,  any
column  or  condition  that  meets  the Method 18 criteria for peak  resolution  is
considered  acceptable.  A particular GC column is recommended based on current EPA
methodology;  where  EPA  methodology  does  not  exist,  methodology  provided  by
organizations other than the EPA is used for rating.  Kovats Retention Indices were
previously used to identify unknown  compounds by comparison of the measured KRI(s)
for a compound to catalogued KRI's  for  the various columns.  In performing Method
18, KRI's can be useful  in  selecting  a GC column which will effectively separate
two (or more) target compounds and/or interferents in an air sample.   In  Table D,
the first number shown for each compound refers to the literature reference for the
column and column conditions suggested for the  recommended  sampling  method (when
available);  the letter(s) associated with this number cross-references the List of
Referenced  Columns  following  Table  D.   Listed  next  for each compound are the
columns  and  conditions  suggested for sampling methods with an acceptable rating;
additional references are provided  for  columns  used for analysis of the selected
compounds under laboratory conditions.  Supplementary references  provide KRI's (in
parentheses) for certain compounds.  As an example of how to use Table D, the entry
for  benzene  is  "12-s,  t;  9-k; 13-u; 4-p; 39-d(658), e(557), i(1039),  h(1104),
v(963)."  This means that the column described in citations s and t in the Table  D
List of Referenced Columns was specified in the method described  in  Reference 12;
the  column described in citation k in the List of Referenced Columns was specified
in the  method  described in Reference 9; the column described in citation u in the
List was specified in the method described in Reference 13; the column described in
citation p in the List was specified in the method  described  in  Reference 4;  and
O

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                                                                  Section No. 3.16
                                                                  Date June  30, 1988
                                                                  Page 7

 the columns described in citations d,  e,  i,  h,  and  v in  the List  were specified  in
 the method described  in  Reference  39-   The   KRI's for  each   column  under the
 conditions given in the List are shown in parentheses.
      The  user  should be aware that interfering compounds  may   exist  in source
 samples.  Some method development work, using the required presurvey sample, may be
 necessary to optimize separation of the compounds of interest from the interfering
 compounds present in  a  source  sample.   As discussed later in Section 3-16.5. any
 column that will provide  an  acceptable   resolution of the compounds can  be used.
 Only packed columns  are  described  in  Table   D   since these   are  more  commonly
 available  to  source  test  analysts than capillary  columns.   However,  capillary
 columns are permitted in Method 18 for analysis.
      Table E shows  the GC calibration  preference for each  compound  based on the
 technique  used  for  sampling.    Where   appropriate,  the  source of  calibration
 standards  is  also  shown.   For each-compound,  the calibration technique shown  is
 rated  either:    (1)   recommended,   (2)   acceptable,  (3)  theoretical,   (4)   not
 recommended,  or (5)  unknown.   A particular  calibration  technique is rated  based on
 current EPA  methodology.    Where  EPA methodology  does  not  exist,  methodology
 provided by organizations other than the   EPA is used for rating.  As an example on
 how  to  use Table E,  the rating for benzene is "R-12 (1806)" for gas cylinders,  "N"
 for  gas  injection into a Tedlar bag,  "A-12"  for  liquid injection  into a Tedlar bag,
 "R-9,13"  for preparation  of  the  standard   in  desorption  liquid,  and   "T"  for
 preparation of  the  standard   on  an adsorption  tube followed by desorption.  This
 means that  gas  cylinders  assayed and certified against National Bureau of Standards
 (NBS) gaseous   Standard  Reference   Material  (SRM)   1806  using   EPA  Traceability
 Protocol  No.  1  (Reference 5)  are recommended  as  the calibration standard for direct
 interface and Tedlar bag samples  with  Reference  12  providing further information on
 the  source  of the calibration standard; preparation of calibration standards by gas
 injection  into  a  Tedlar  bag  is  not  recommended;  preparation of  calibration
 standards   by   liquid   injection into a Tedlar bag is  acceptable and Reference 12
 provides   further   information;   preparation  of calibration   standards   in  the
 desorption  liquid is the  recommended procedure for   use  with  the adsorption tube
 methods described in References  9 and  13;  and preparation of calibration standards
 on adsorption tubes followed  by  desorption is  theoretically  valid  for  use  with
 adsorption  tube samples.
     Because the number of organic  compounds  of  interest to EPA and state and local
 agencies  is increasing, and  since EPA plans  to   conduct  methods development and
validation  studies  for  many of  the organic compounds  identified here as well as for
 additional  compounds identified  in  the future,   the Method  Highlights  portion  of
Section 3-16 will be updated  every two or  three years.  As with all other revisions
 of Volume III of the Quality  Assurance Handbook, those  individuals whose names are
 in   the Record Distribution System will automatically receive  the  updated  Method
Highlights section.
     For compounds not  currently  listed  in the  tables,  Figure 0.1 may be used as a
 general guide in selecting appropriate sampling  techniques.   However,  any technique
used must meet the criteria described  in detail in  the subsequent  sections.
     The Method Description  (Sections  3.16.1  to 3.16.9)   is  based  on the detailed
 specifications in the Reference  Method   (Section  3-16.10)   promulgated  by EPA on
October 18, 1983 and corrections and revisions promulgated February 19,  1987.  '

1.  Procurement of Apparatus and Supplies

     Section  3-16.1  gives  specifications,   criteria,  and  design features  for  the

-------
               CONCENTRATION
               >1PPMV
  CHARACTERIZE
  STATIONARY
  SOURCE  	
  ORGANIC
  COMPOUND
  EMISSIONS
                             LOW TEMPERATURE
                             LOW MOISTURE (< 1%)
v
               CONCENTRATION
               <, 1PPMV
                             MEDIUM TEMPERATURE
                             MEDIUM MOISTURE (> 3%)
HIGH TEMPERATURE
HIGH MOISTURE (> 10%)
                             SEMIVOLATILE
                                            MM5
                              VOLATILE
                                            VOST
                                                  NONPOLAR
                                                  POLAR
                                                  NONPOLAR
                                                  POLAR
                     HIGH CONCENTRATION
                                         TEDLAR BAG
                                         ADSORPTION TUBE
                                         DIRECT INTERFACE
                                         DILUTION INTERFACE
                                         ADSORPTION TUBE
                                         DIRECT INTERFACE
                                         DILUTION INTERFACE

                                         HEATED TEDLAR BAG
                                         ADSORPTION TUBE
                                         DIRECT INTERFACE
                                         DILUTION INTERFACE
                                         ADSORPTION TUBE (SILICA)
                                         DIRECT INTERFACE
                                         DILUTION INTERFACE
                                         DILUTION INTERFACE
                                                   LOW CONCENTRATION
                                                                       DIRECT INTERFACE
              Figure 0.1.  General scheme for selection of appropriate sampling techniques.
                                                                          "0 O W
                                                                          C3 P Q
                                                                          OT ft O
                                                                          (0 (B ct
                                                                                                         LO •
                                                                                                         O
                                                                                                         • LO
                                                                                                          CO
                                                                                                          OO
                                                                              O\
      O
                         O
O

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                                                                 Section No. 3.16
                                                                 Date June 30, 1988
                                                                 Page 9

 required equipment and materials.  The sampling apparatus for Method 18  is divided
 according  to   the  different   sampling  approaches.   This section can be used as a
 guide  for  procurement and  initial  checks of equipment and supplies.   The  activity
 matrix (Table  1.1) at  the end of  the section is a summary of the details given  in
 the  text and can be used as a  quick  reference.

 2.   Presampling Preparations

     Section 3-16.2 describes  the  required calibration procedures for the Method 18
 sampling   equipment.   Section  3-16.3 describes the presampling operations and the
 acquisition of supplies and equipment  needed for -the sampling.  Preliminary survey
 sampling is discussed, including a description of classes of organic  compounds and
 the  presurvey  sampling techniques  that  are  generally  used to obtain a sample for
 evaluation purposes.   The  presurvey  sampling  and  analytical methods are  then
 described.  Finally, how to select  the  proper  sampling  and analytical equipment
 based  on the presurvey data is discussed.   The  preliminary survey and presanpling
 preparation forms (Figures 3-2  and  3-5 of Section 3.16.3) can be used as equipment
 checklists.  Suggestions for packing the  equipment  and supplies for shipping are
 given  to help  minimize breakage  and  reduce contamination.
     Activity  matrices  for  the  calibration  of  equipment  and  the  presampling
 operations (Tables 2.1 and 3-1)  summarize the activities detailed in the text.

 3.   On-Site Measurements

     Section   3-16.4 describes several sampling techniques.  The use of the presur-
 vey  sample analyses and the sampling matrix tables (Tables A  through  E)  provides
 the  user with  the required information to select the proper sampling  technique.  A
 checklist  (Figure 4.8) is  an easy  reference for  field  personnel  to  use  in  all
 sampling activities.   Sampling  and analyses  using  the direct interface and the
 dilution interface methods  are  both  conducted  on-site;  however, to provide for
 greater consistency of presentation, the analytical procedures are presented in the
 Posttest Operations Section with those for the other sampling techniques.

 4.   Posttest Operations

     Section 3-16.5 describes  the  analytical procedures and the posttest activities
 for  checking the equipment.  The initial analytical procedure of sample preparation
 is shown based  on  the  sampling  technique  used  and includes the procedures for
 preparation  of the calibration  standards.   The second procedure discussed  is  the
 method of introducing a known  volune of sample into the  GC and this is followed by
 a discussion of GC operations.    The detailed analytical  procedures   can be removed
 for use as an easy reference in  the  laboratory.    An  activity  matrix (Table 5.1)
 summarizes the postsampling operations.
     Section 3-16-6 describes calculations,  nomenclature,   and  significant  digits
 for  the  data  reduction.    A   programmed   calculator  is  recommended  to  reduce
 calculation errors.
     Section 3-16-7  recommends  routine  and preventive maintenance programs.   The
programs are not required,  but  their use  should  reduce equipment downtime.

 5-  Auditing Procedures

     Section  3-16.8  describes performance  and  system audits.   Performance   audits
for both  the  analytical phase and the data processing  are described.  A checklist

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                                                                 Section No.  3-16   ^-s.
                                                                 Date June 30,  1988 (    )
                                                                 Page 10            V_y

(Figure 8.2) outlines a system audit.
     Section 3.16.9 lists the primary standards to which  the  working standards or
calibration standards should be traceable.

6.  References

     Section 3-16.10 contains  the promulgated Method; Section 3-16.11 contains the
references used throughout this text; and Section 3-16.12 lists  all the data forms
in Section 3-16 and contains copies of blank  data  forms for those shown completed
in  the  text.   These  may be removed from  the  Handbook,  copied,  and  used  in
performing the method.   Each  form  has a subtitle [e.g., M18-2.5 (Figure 2.5)] to
assist  the  user  in  locating  the  same  completed form in  the  text.   Several
checklists  are not completed in the text and and therefore not reproduced in  this
section.
                                                                                    O
                                                                                     o

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                                                                              Section No.  3.16
                                                                              Date June 30, 1988
                                                                              Page 11
     TABLE A.  STATUS OF SELECTED ORGANIC COMPOUNDS FOR METHOD 18 SAMPLING  AND  ANALYSIS TECHNIQUES
Chemical Abstracts Name
                                   Synonyms
                                                         Formula
                                                                     CAS  No.
                                                                               Method
                                                                               Class
                                                                                       EPA Audit
                                                                                       Cylinder(ppm)'
                                               Alcohols
Methanol
Ethanol
Isopropyl Alcohol
n-Propyl Alcohol
n-Butyl Alcohol
Methyl Alcohol
Ethyl Alcohol
2-Propanol
1-Propanol
1-Butanol
CH.O
C-fl,0
C3H8°
w
C4H10°
(67-56-D
(64-17-5)
(67-63-0)
(71-23-8)
(71-36-3)
0-6
0-7
0-7
0-8
0-8 ;
30-80
No
No
No
No
                                               Alkanes
Cyclohexane
Hexane

Ethylene
Propylene

1,3-Butadiene
Hexachlorocyclopentadiene
1 C6H12
1 C$Hl4
Alkenes
Ethene I CjIK
Propene ] C.H/.
Dienes
Butadiene j C^H,
Perchlorocyclopentadlene 1 C -Cl,
| (110-82-7)
| (110-54-3)

j (74-85-1)
1 (115-07-1)

| (106-99-0)
| (77-47-4)
0-9
0-9

:

D-10
0-11
| 80-200
J20-90.1000-3000

1 5-20,300-700
I 5-20,300-700

| 5-60
j No
                                               Aromatic
Benzene
Mesitylene
Ethylbenzene
Cumene
Xylene (m-,o-,p-)
Toluene
Styrene
2-Naphthylamine
Benzol
1 , 3,5-Trimethylbenzene

1-Methylethylbenzene
Dimethylbenzene
Methylbenzene
Ethenylbenzene
2-Naphthylenanine
C6H6
C9«12
r'u
V'R™1 n
P H
Q 12
C'u
81O
r* ^»« *"
C7H8
p'u
88
«SoV
(71-43-2)
(108-67-8)
(100-41-4)
(98-82-8)
(1330-20-7)
(108-88-3)
(100-42-5)
(91-59-8)
T-12
N
0-13
0-13
0-13
0-9.13
0-13
O-14
5-20,6o-4oo
NO
No
No
5-20,300-700
5-20,100-700
No
No
                                               Ketones
Acetone
Methyl
Methyl
Ethyl Ketone
Isobutyl Ketone
2-Propanone
2-Butanone
4-Methyl-2-pentanone
C H60
C4H8°
(67-64-1)
(78-93-3)
(108-10-1)
0-15
0-16
0-15
No
30-80
5-20
Epoxides
Ethylene Oxide
Propylene Oxide
                               Epoxy Ethane
                               1,2-Epoxy Propane
C2H4°
|  (75-21-8)   | 0-17  |   5-20
I  (75-56-9)   1 0-18  I 5-20,75-200
                                               Sulfides
bis(2-Chloroethyl)  Sulfide
                               Mustard Gas
                                                                   (505-60-2)
                                                                                           No

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                                                                                 Section No.  3-16
                                                                                 Date June  30,  1988
                                                                                 Page 12
o
TABLE A.  (Continued)
Chemical Abstracts Name
1 1
Synonyms | Formula | CAS No.
Method
Class
EPA Audit
Cylinder(ppm)*
Halogenated
Ethylidene Chloride
Ethylene Dibromlde
Ethylene Dichloride
Propylene Dichloride
1,1,1-Trichloro ethane
Bromodichlorome thane
Chlorodibromome thane
Chloroform
Carbon Tetrachloride
Dichlorodifluoromethane
Methyl Bromide
Methyl Chloride
Methylene Chloride
Tetrachloroethylene
Bromoform
Trichloroethylene
Trichlorotrifluoroethane
Vinylidene Chloride
Ethyl Chloride
Chlorobenzene
Vinyl Chloride
l,2-Dibromo-3-chloropropane
1 ,1-Dichloroe thane
1 , 2-Dibromoethane
1,2-Dichloroethane
1,2-Dichloropropane
Methyl chloroform


Trichlorome thane
Tetrachlorom ethane
Preon 12
Bromomethane
Chi orome thane
Dichlorom ethane
Perchloroethylene
Tribromome thane
Trichloroethene
Freon 113
1,1-Dichloroethene
Chloroethane
Mono Chlorobenzene
Chloroe thylene
DBCP
C2H4C12
C2H4Br2
C2H4C12
CKC12
C^H.Cl
cfifirci
CHBr CI
CHC1
CCl,
CC1 F
CH fir
CH^Cl
CH,C1
C Cl
CHBr
C_HCf
C*C1 J
C2H2 2
C H Cl
cf H Cl
C2H1C1
C_H_Br_Cl
(5-34-3)
(106-93-4)
(107-06-2)
(78-87-5)
(71-55-6)
(75-27-4)
(124-48-1)
(67-66-3)
(56-23-5)
(75-71-8)
(74-83-9)
(74-87-3)
(75-09-2)
(127-18-4)
(75-25-2)
(79-01-6)
(76-13-D
(75-35-4)
(75-00-3)
(108-90-7)
(75-01-4)
(96-12-8)
0-19
0-20
T-21
0-22
T-21
N
N
T-23
T-23
0-24
0-25
O-26
T-2?
T-21
0-19
T-21
T-21
0-28
O-29
0-19
R-30
0-37
No
5-20,50-300
5-20,100-600
3-20,300-700
5-20
No
No
5-20,300-700
5-20
No
No
No
1-20
5-20.300-700
No
5-20,100-600
5-20
5-20,100-600
No
5-20
5-30
No
Method Classification Code
  R " Reference -   EPA promulgated method.
  T • Tentative -   EPA method development  complete;  EPA  reference available.
  D * Development - EPA method currently under  development.
  0 * Other -       Method development  completed  by  organizations other than EPA; reference available.
  N « None -        No reference  available;  recommendation baaed on experience.

     The codes in the method classification  column describe  the current status of a sampling and analysis
method for each selected compound.   For example,  the  method  classification code for benzene is: T-12.
This means the current method for benzene is a  tenative EPA  method with development complete and the
reference for the method is citation number  12  in Section 3.16.11.

* The availability of EPA audit cylinders is shown in  this column where:

   (   ) * Audit cylinders for this particular  compound are  available from EPA in the concentration ranges
           indicated (Reference 4).

     No  •= Audit cylinders for this particular  compound are  not available from EPA.  The source tester must
           obtain audit  gas cylinders from commercial  gas vendors certified by Independent analysis to be
           within 5 percent of the  concentration  claimed by  the vendor.
                                                                                                            O
                                                                                                             o

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                                                                         Section No.  3.16
                                                                         Date June 30,  1988
                                                                         Page 13
TABLE  B.   METHOD 18  SAMPLING TECHNIQUES FOR SELECTED ORGANIC COMPOUNDS

Selected Compounds

Interface Bag*
1 Adsorbent Tubes
Charcoal* | Other ••
and Desorption Liquid
| Desorption Liquid**"
                                          Alcohols
Methanol
Ethanol
Isopropyl Alcohol
n-Propyl Alcohol
n-Butyl Alcohol
T
T
T
T
T
N
N
N
N
N
N
T-7
T-7
T-8
T-8
A-6; Silica Gel
-
-
-
-
Distilled Water
1% 2-Butanol in CS
IX 2-Butanol in CS^
Carbon Disulfide
Carbon Disulfide
                                          Alkanes
Cyclohexane
Hexane

Ethylene
Propylene

1,3-Butadiene
Hexachlorocyclopentadiene
T | U 1 T-9 | - |
T j U j T-9 j - j
Alkenes
T N | U | U |
T U j U* | U |
Dienes
T A-10 1 A-Al | U j
T U I N j A-ll; Porapak |
Carbon Disulfide
Carbon Disulfide

U
U

Carbon Disulfide
Hexane
                                          Aromatic
Benzene
Mesitylene
Ethylbenzene
Cuciene
Xylene (m-,o-,p-)
Toluene
Styrene
2-Napthylamine
T
T
T
T
T
T
T
T
R-12
U
U
u
u
u
u
u
T-9. 13
u
T-13
T-13
T-13
T-9, 13
T-13
T-lA
_
-
-
-
-
-
-

Carbon Disulfide
U
Carbon Disulfide
Carbon Disulfide
Carbon Disulfide
Carbon Disulfide
Carbon Disulfide
Carbon Disulfide
                                          Ketones
Acetone
Methyl Ethyl Ketone
Methyl Isobutyl Ketone
T
T
T
N
N
N
T-15
N
T-15
A-16; Ambersorb
Carbon
Carbon
Carbon
Disulfide
Disulfide
Disulfide
Epoxides
Ethylene Oxide
Propylene Oxide
T
T
A
U
T-l?
T-18

99:1 Benzene:CS.
Carbon Disulfide
Sulfldes
bis(2-Chloroethyl) Sulfide
T
U
U
U
U
                                                                                  (continued)

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                                                                                  Section  No.  3.16
                                                                                  Date June 30,  1988
                                                                                  Page 14
                                                                                      o
  TABLE B.  (Continued)

Selected Compounds

Interface

Bag*
Adsorbent Tube*
Charcoal* | Other ••
and Desorptlon Liquid
| De»orptlon Liquid"**
                                                  Halogenated
Ethylidene Chloride
Ethylene Dibromlde
Ethylene Bichloride
Propylene Diehlorlde
1 , 1,1-Triehloroe thane
B ronodich lor ooe thane
Chlorodibromooe thane
Chloroform
Carbon Tetrachloride
Dlchlorodif luorome thane
Methyl Bromide
Methyl Chloride
Methylene Chloride
Tetraehloroethylene
Bromoforn
Trlchloroethylene
Trichlorotr if luoroe thane
Vlnylidene Chloride
Ethyl Chloride
Chlorobenzene
Vinyl Chloride
1 , 2-Dibromo-3-chloropropane
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
U
N-31
• R-21
U
R-21
U
U
R-23
R-23
U
U
U
R-27
R-21
U
R-21
R-21
U
U
U
R-30
U
T-19
T-20
T-19
T-22
T-19
U
U
T-19
T-19
T-24
T-25
T-26
T-32
T-33
T-19
T-3«
T-35
T-28
T-29
T-19
T-36
T-37
„
-
-
-
-
-
.
-
-
-
-
-
-
-
-
-
-
-
-
-
-

Carbon Dltulflde
99U BenzenetMeOH
Carbon Dlsulflde
15X Acetone in Cyclohexane
Carbon Dlsulflde
U
U
Carbon Dlculfide
Carbon Diaulfide
Methylene Chloride
Carbon Disulfide
Methanol
Carbon Diaulfide
Carbon Diaulfide
Carbon Diaulfide
Carbon Diaulfide
Carbon Dlsulflde
Carbon Disulfide
Carbon Disulfide
Carbon Diaulfide
Carbon Disulfide
Carbon Diiulfide
Rating Code
 R • Recommended.
 A * Acceptable.
 T • Theoretical.
                                                                                                            O
Based on actual source tests experience  (sampling  and  analysis)  this method is
valid and Is the method of choice among  Method 18  users.

Based on actual source tests or similar  source test  experience  (sampling  and
analysis), this method is valid.  The tester  must evaluate  for specific  test.

Method haa no documented experience, but in  theory could be  valid.
 N « Not Recommended.  Based on actual source  tests  or  similar  source  test experience and/or theory, this
                      method is invalid.
 U » Unknown.
                      Method has  no documented  experience  and  the  theoretical aspects of sampling by this
                      method are  inconclusive.   The  tester must demonstrate that this sampling method is
                      valid.
     The rating codes for sampling are  based on  the  extent of method validation.  For example, the rating
code for benzene is:  T;  R-12;  A-9,13.   This  means  that direct interface is theoretically possible for
benzene, but no documented experience has  been found; Tedlar bags are the recommended sampling method for
benzene by the tenatlve  EPA method referenced in citation 12 in Section 3.16.11; and sampling with
charcoal adsorption tubes is acceptable following  the two methods referenced in citations 9 and 13 in
Section 3.16.11.

  * » If condensibles exist, use  the procedure described in Section 3.16.A.

 •• = Solid sorbents  other than charcoal recommended.
      The recommended desorption  solution  is  given  In thia column.
      priate reference  for  details.
                                             Analyst should consult the appro-
                                                                                                             O

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                                                        Section  No. 3.16
                                                        Date June 30,  1988
                                                        Page 15
TABLE  C. GC DETECTORS FOR SELECTED ORGANIC COMPOUNDS  BY METHOD 18
Selected Compounds
Gas Chrornatograph Detector *
FID
ECD
FID
ELCD
Alcohols
Methanol
Ethanol
Isopropyl Alcohol
n-Propyl Alcohol
n-Butyl Alcohol
R-A.6
R-7
R-7
R-8
R-8
N
N
N
N
N
T-38
T-38
T-38
T-38
T-38
N
N
N
N
N
Alkanes
Cyclohexane
Hexane
R-A.9
R-A.9
N
N
T-38
T-38
N
N
Alkenes
Ethylene
Propylene
A-A
A-A
N
N
T-38
T-38
N
N
Dlenes
1,3-Butadlene
Hexachlorocyclopentadiene
R-A.10.Al
R-ll
N
T
T-38
u
N
T
                               Aromatic
Benzene
Mesltylene
Ethylbenzene
Cuoene
Xylene (o-,m-,p-)
Toluene
Styrene
2-Napthylamine
R-A.12
T
R-13
R-13
R-A.13
R-A.9.13
R-13
R-lA
N
N
N
N
N
N
N
N
T-38
T-38
T-38
T-38
T-38
T-38
T-38
U
N
N
N
N
N
N
N
N
                               Ketones
Acetone
Methyl Ethyl Ketone
Methyl Isobutyl Ketone
R-15
R-A.16
R-A.15
N
N
N
T-38
T-38
T-38
N
N
N
Epoxides
Ethylene Oxide
Propylene Oxide
R-A,
R-A,
17
18
N
N
T-38
T-38
N
N
Sulfides
bls(2-Chloroethyl) Sultide
U
U
U
U
(continued)

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                                                                            Section No.  3.16
                                                                            Date  June  30,  1988
                                                                            Page  16
                                                                                    o
TABLE C.   (Continued)
1
1 	 ....
Selected Compounds | FID
Halogenated
Gas Chromatograph Detector •
| ECD | PID |


ELCD

Ethylidene Chloride
Ethylene Dlbromlde
Ethylene Dlchlorlde
Propylene Dlchlorlde
1,1,1-Trlchloroethane
Bromodlchl or one thane
Chlorodlbromomethane
Chloroform
Carbon Tetrachlorlde
Dichlorodif luorome thane
Methyl Bromide
Methyl Chloride
Methylene Chloride
Tetrachloroethylene
Bromoform
Trlchloroethylene
Trlchlorotrlfluoroethane
Vlnylldene Chloride
Ethyl Chloride
Chlorobenzene
Vinyl Chloride
1 , 2-Dlbromo-3-chloropropane
R-19
A-4
R-4.21
A-4
R-4.21
U
U
R-4.23
R-4,23
R-24
R-25
R-26
R-4,27.32
R-4,21
R-19
R-4,21
R-4.21
R-4.28
R-29
R-4,19
R-4,30
U
T
R-20
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
R-37
U
U
T-38
T-38
U
U
U
T-38
T-38
N-38
T-38
T-38
T-38.
T-38
T-38
T-38
N-38
T-38
T-38
T-38
T-38
u
T
T
T
R-22
T
T
T
A-23
A-23
T
T
T
T
T
T
T
T
T
T
T
T
T
Rating Code
 R * Recommended.
 A • Acceptable.
 T «= Theoretical.
     Not Recommended.
     Unknown.
Based on actual source tests experience (sampling and analysis)
this method is valid an is the method of choice  among Method  18
users.

Based on actual source tests or similar source  test  experience
(sampling and analysis),  this method is valid.  The tester  must
evaluate for specific test.

Method has no documented  experience, but in theory could be
valid.

Based on actual source tests or similar source  test  experience
and/or theory, this method is Invalid.

Method has no documented  experience  and the heoretical  aspects
are not conclusive.  The  tester must demonstrate  that  this
detection method is valid.
     The rating codes  for GC  detectors  are  based on  the detector specified in the method
that is referenced.   For example,  the rating  code  for benzene is: R-4,12; N; T-38; N.
This means that the  FID is recommended  for  detection of benzene by both references 4 and
12 cited in Section  3-16.11;  the  ECD and  the  ELCD  are not recommended for benzene; and
detection of benzene with a PID  is  theoretically possible based on the ionization
potential found in reference  38.

•  The following abreviations  are  used  for  the gas chromatography detectors:
   FID  = Flame  Ionization  Detector
   ELCD • Electroconductivity  Detector
             (Hall  Detector)
                                 ECD   «  Electron Capture Detector
                                 PID   »  Photoionization Detector
                                 (with lamps up to 11.7 electron
                                  volta)
                                                                                                          O
o

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                                                                                  Section  No.  3.16
                                                                                  Date June 30,  1988
                                                                                  Page 1?
TABLE D.  PACKED COLUMNS SUITABLE FOR ANALYSIS  OF  SELECTED  ORGANIC  COMPOUNDS  BY GAS CHROMATOGRAPHY
  Selected Compounds          |  Column Reference,  Type  and  Conditions,  and  Kovats Retention  Indices*
 ISBBBBBBBBKBBBBBB&XBSBSSBBBBBBBBBBZSZBBBHBBBBBBBSBBEXBBSBBBMBBBBSBSBBSBSBBBEBBXXBBXBSS —SSSEK —B = SSCBB:SS== = =:
                                                          Alcohols

  Methanol                     6-a;  A-b,  c;  39-d(370),  e(33D.  f(426)
  Ethanol                       7-g 	,-
  I«opropyl Alcohol             7-g;  39-d(A77),  e(39°),  f(576).  hdoA?).  i(loA6)
  n-Propyl Alcohol              8-J;  39-e<387>.  f(533)
  n-Butyl  Alcohol               8-j ;  39-d(6A9)

                                                          Alkanes

  Cyclohexane                 |  9-k;  4-1;  39-d(66?),  e(511),  f(6l9)
  Hexane                      |  9-k;  A-n;  39-d(6oO).  e(600),  f(600)

                                                          Alkenea

  Ethylene                   I  4-n                     ._
  Propylene                  j  4-n                     '

                                                          Diene*

  1,3-Butadlene               |  lO-o;  4-p,  q, 4l-nnn
  Hexachlorocyclopentadiene   |  11-r

                                                          Aromatic

  Benzene                       12-s.  t: 9-k; 13-u; 4-p;  39-1(658),  e(557).  i<1039). h(1104>, v(9&3)
  Mesitylene
  Ethylbenzene                  13-u;  4-d(869),  e(573).  i(128l)
  Cumene                        13-u;  A-i(13l8)
  Xylene  (o-.m-.p-)             13-w;  A-x;  39-d(m  * 876,  p  *  877. o  * 900),  i(m  * 1297. p  B  1312. o «  1353)
  Toluene                       9-k;  13-w;  A-p;  39-d(?6l),  h(1136),  i(1201).  v(!060)
  Styrene                       13-w;  39-i(lAl9)
  2-Napthylamine                lA-y
 BZBBBBaBBBBBBBKKBBBBKBX«XBBBBBBttSB = B = = &«S9IKSSBBBXBB«KBSBBBaBBBBBBBBBKIIBBBXBBZBBBIBBBBBte = BBSSSBBBSSSSBSS = SS
                                                          Ketones

  Acetone                     |  15-z;  A-e(380),  f(636).  h(1009). h(1091)
  Methyl Ethyl Ketone         j  16-aa;  A-bb; 39-d(579).  e(A76),  f(6AA), h(1087), 1(1158),  v(927)
  Methyl Isobutyl Ketone      |  15-z;  A-cc; 39-
-------
                                                                                 Section No.  3.16
                                                                                 Date June  30, 19&
                                                                                 Page 18
                                                                          o
TABLE D.   (Continued)

 Selected Compounds
|  Column Reference,  Type and Conditions, and Kovats Retention Indices*
                                                        Halogenated
 Ethylidene  Chloride
 Ethylene  Dlbronlde
 Ethylene  Dlchloride
 Propylene Dlchloride
 1,1,1-Trichloroe thane
 Bromodichloronethane
 Chiorodibromoraethane
 Chloroforn
 Carbon Tetrachlorlde
 Dichlorodlfluoromethane
 Methyl Bromide
 Methyl Chloride
 Methylene Chloride
 Tetrachloroethylene
 Bromoform
 Trichloroethylene
 Trichlorotrifluoroethane
 Vinylidene  Chloride
 Ethyl  Chloride
 Chlorobenzene
 Vinyl  Chloride
 1,2-Dibromo-3-chloropropane
  20-hh
  21-11
  22-kk
  21-11
  23-11
  23-11
  24-pp
  25-qq
  26-rr
  27-«s.
  21-11;
  19-ww
  21-11;
  21-11;
  28-zz;
  29-11
  19-bbb
  30-ccc
  37-ggg
 39--  e(574),  f<736).  h(10$6),  1(1105).  v(1039)

 34-xx;  4-1;  39-d(695),  e(546),  f(665),  h(1009),  i(1068),  v(1004)
 35-yy;  4-oo
 4-JJJ;  39-h(760),  i(792),  v(738)

  4-kkk;  39-d(842).  h(1347)
  ddd;  36-eee;  4-fff
O
  The  GC  column  references,  column  types  and  conditions, and  Kovats Retention  Indices  (if available) are
  shown  in  this  column.   The first  reference  shown  for  each compound  is  for  the  column  and conditions
  suggested  for  the  recommended  sampling  method  (when available),  followed by  the  column and conditions
  suggested  for  sampling  methods with  an  acceptable  rating.   Additional  references are  given when
  available  for  columns used for analysis of  the  selected  compound under laboratory  conditions.  Some
  additional  references provide  Kovats Retention  Indices for  selected compounds.   For  example, the
  reference  code  for benzene is:  12-s,  t; 9-k; 13-ui 4-p;  39-d(658).  e(557), 1(1039),  h(1104), v(9&3).
  This means  that  for  benzene the columns described  in  citations s and t in  the  List of Referenced
  Columns  (following Table 0) were  specified  in  the  method described  In  citation 12  in  Section 3.16.11;
  the  column  described in citation  k in the List  of  Referenced Columns was specified in the method
  described  in citation 9 in Section 3-l6.ll;  the column described in citation u was specified in the
  method  descibed  In citation 13 in Section 3.16.11; the column described in citation  p was specified in
  the  method  described in citation  4 in Section  3.16.11; and  the columns described in  citations d, e, 1,
  h.and v were specified  in  the  method described  in  citation  39 in Section 3.16.11.  Where available, the
  Kovats  Retention Indices for each of the columns under the  conditions  given  in their  respective
  references  are  given in parentheses-

  Note: Any  column or  conditions that  meet the Method 18 criteria  for peak resolution  are considered
  acceptable.
                                                                                                       O

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                                                                Section No.  3.16
                                                                Date  June  30,  1988
                                                                Page  19
APPENDIX I to TABLE D.
             LIST OF REFERENCED COLUMNS WITH SUGGESTED OPERATING CONDITIONS
      60/80 mesh Tenax, operated isothermally at 80°C.
      Chromasorb 101, operated isothermally at 50 C.
                              SP-2100 on Carbopack C,  operated isothermally at
(a).
(b).
(c).  0.2% Carbowax 1500/0.:
        60°C.
(d).  20% SP-2100/0.1% Carbowax 1500 on 100/200 mesh Supelcoport, operated
        isothermally at 70°C.
(e).  Carbopak C-HT 80/100 mesh, operated isothermally at 90 C.                ~
(f).  Porapak T 80/100 mesh,  operated isothermally at l40°C.
(g).  0.2% Carbowax 1500 on 60/80 mesh Carbopack C, temperature programmed from 65°
          to 70°C.
(h).  15% tetracyanoethylated pentaerythritol on 60/80 mesh Chromasorb P-AW,
        operated isothermally at 80 C.
(i).  15% tetracyanoethylated pentaerythritol on 60/80 mesh Chromasorb P-AW,
        operated isothermally at 100 C.
(j).  10% SP-1000 on 80/100 mesh Chromasorb WHP, temperature programmed from 75°C.
(k).  20% SP-2100 on 80/100 mesh Supelcoport, operated isothermally at 40° or  -
        70 C or temperature programmed from 50 C, depending on other anal-
        ytes of interest.   See referenced method for details.
(1).  10% OV-101 on Chromasorb WHP, operated isothermally at 100 C.
(m).  10% OV-101 on Chromasorb WHP, operated isothermally at 60° or 100°C.
(n).  Durapak n-octane on Porasil C, operated isothermally at 30 C.
(o).  1% SP-1000 on Carbopack B, operated isothermally at 55°C for 12 minutes.
(p).  10% OV-101 on Chromasorb WHP, operated isothermally at 60°C.
(q).  0.1% SP-1000 on Carbopack C, operated isothermally at 90°C.
(r).  3% OV-1 on 100/120 Gas  Chrom Q, operated isothermally at 135 C.
(s).  For benzene in the presence of aliphatics, 10% 1,2,3-tris (2-cyanoethoxy)
        propane (TCEP) on 80/100 Chromasorb P AW.
(t).  For benzene with separation of xylene isomers, 5% SP-1200/1.75% Bentone 34  on
        100/120 mesh Supelcoport,  operated isothermally at 75°C.
(u).  10% OV-275 on 100/120 mesh Chromasorb W-AW, operated isothermally at 50°C or
        temperature programmed starting at 50 C for 3 minutes followed by
        15°C/min increase to  200°C.
(v).  10% FFAP on 80/100 Acid-washed Chromasorb W, operated isothermally at 125°C.
(w).  10% OV-275 on 100/120 mesh Chromasorb W-AW, operated isothermally at 50°
        or 100 C or temperature programmed starting at 50°C for 3 minutes followed
        by 15°C/min increase  to 200 C.
(x).  For meta-xylene, 10% OV-101  on Chromasorb WHP, operated isotheramlly at 60°,
        120°, or 140°C.
(y)•  3% OV-225 on 80/100 mesh Supelcoport,  operated isothermally at 163 C.
(z).  10% SP-2100/0.1% Carbowax 1500 on 100/120 mesh Supelcoport, temperature
        programmed from 50° to 170°C at 10°C/min.
(aa).  20% SP-2100/0.1% Carbowax 1500 on 100/120 mesh Supelcoport, operated isother-
        mally between 55  and 75°C.
(bb).  Chromasorb 101,  operated isothermally at 180 C.
(cc).  0.1% SP-1000 on Carbopack C,  operated isothermally at 180 C.
(dd).  50/80 mesh Porapak Q, operated isothermally at 135 C.

(continued)

-------
                                                              Section No.  3«l6
                                                              Date  June  30,  1988
                                                              Page  20
                                                                                       X-*v
(ee).   80/100 mesh Porapak QS,  operated isothermally at  150°C.
APPENDIX I to TABLE D. (Continued)

(ee).  80/100 mesh Porapak QS, ope
(ff).  50/80 mesh Porapak Q, operated isothermally at 145UC.
(gg).  10% SP-1000 on 80/100 mesh Supelcoport, operated isothermally at 50 C.
(hh).  3% OV-210 on 80/100 mesh Gas Chrom Q, operated isothermally at 50 C.
(ii).  20% SP-2100/0.1% Carbowax 1500 on 100/200 mesh Supelcoport, operated
         isothermally at 100°C.
(jj).  10% SP-1000 on 80/100 mesh Supelcoport, operated isothermally at 70 C.
(kk).  3% Carbowax 1500 on 60/80 mesh Chromasorb WHP, operated isothermally at
         50°C.
(11).  1% SP-1000 on Carbopack B, operated isothermally at 120 C.
(mm).  10% SP-1000 on 80/100 mesh Supelcoport, operated isothermally at 75 C.
(nn).  10% SP-1000 on 80/100 mesh Supelcoport, operated isothermally at 60 C.
(oo).  10% SP-1000 on 80/100 mesh Supelcoport, operated isothermally at 100 C.
(pp).  80/100 mesh Chromasorb 102, operated isothermally at 110 C.
(qq).  10% FFAP on 100/120 mesh Chromasorb WHP, operated isothermally at 65 C.
(rr).  80/100 mesh Chromasorb 102, operated isothermally at 100 C.
(ss).  5% OV-101 on 80/100 Chromasorb WAP, operated isothermally at 35 C.
(tt).  10% SP-1000 on 80/100 mesh Supelcoport, operated isothermally between 60
         and 90°C.
(uu).  10% OV-101 on 100/120 mesh Supelcoport, operated isothermally at 90°C.
(w).  10% OV-101 on Chromasorb WHP, operated isothermally at 50° or 100 C.
(ww).  10% SP-1000 on 80/100 mesh Supelcoport, operated isothermally at 130°C.
(xx).  10% OV-101 on 100/120 mesh Supelcoport, operated isoth'ermally at 70°C.           S~\.
(yy).  50/80 mesh Porapak Q, operated isothermally at 150 C.                            I   )
(zz).  100/120 mesh Durapack OPN in silanized glass,  operated isothermally at  65 C.     ^-"
(aaa). 10% FFAP on 100/120 mesh Chroraasorb WHP, operated isothermally at HQ°C.
(bbb). 10% SP-1000 on 80/100 mesh Supelcoport, operated isothermally at 105 C.
(ccc). 80/100 mesh Chromasorb 102, operated isothermally at 100°C.
(ddd). For sources where acetaldehyde is present,  use column cited in (ccc)
         followed by a column  of  20%  GE  SF-96  on 60/80 mesh Chromasorb P  AW or
         80/100 mesh Porapak T connected in series,  operated isothermally at 120 C.
(eee). 10% SE-30 on 80/100 Chromasorb W, operated isothermally at 60°C.
(fff). 0.4% Carbowax on Carbopack C, operated isothermally at 50°C.
(ggg). 1.5 OV-17 plus 1.95% OV-210.
(hhh). 5% OV-101 on Chromasorb WHP, operated isothermally at 60°C.
(iii). 10% OV-101 on Chromasorb WHP, operated isothermally at 50° or 100°C.
(JjJ). 10% OV-101 on Chromasorb WHP, operated isothermally at 100°C or 10% SP-2100
         on Supelcoport,  operated isothermally at 100°C.
(kkk). 10% SP-1000 on 80/100 mesh Supelcoport, operated isothermally at 150°C.
(111). 1% SP-1000 on 60/80 mesh Carbopack, temperature programmed starting at  40 C
         for 3 minutes, followed by 8 C/min increase to 200°C.
(mmm). 15% FFAP on Anakrom A.
(nnn). 10% FFAP on 80/100 mesh Chromosorb W AW-DMCS,  operated isothermally at  52 C.
                                                                                       o

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                                                                  Section No.  3-16
                                                                  Date  June 30,  1988
                                                                  Page  21
TABLE  E.  RECOMMENDED  CALIBRATION TECHNIQUES FOR  SELECTED ORGANIC COMPOUNDS BY METHOD 18
Selected Compounds
Methods for Direct Interface
and Tedlar Bag Samples
Gas
Cylinders
Gas
Injection
Into
Tedlar Bag
Liquid
Injection
Into
Tedlar Bag
Methods for Adsorption
Tube Samples
Prepare
Standard in
Desorption
Liquid
Prepare
Standard
on Tube
and Desorb
                                  Alcohols
Methanol
Ethanol
Isopropyl Alcohol
n-Propyl Alcohol
n-Butyl Alcohol

Cyclohexane
Hexane

Ethylene
Propylene

1,3-Butadiene
Hexachlorocyclopentadiene
T-4
U
U
U
U

T-4
T-A

T-4
T-4

A-10
U
N
N
N
N
N
Alkanes
N
N
Alkenes
U
U
Dienes
R-10
N
U
U
U
U
U

u
u

N
N

N
U
R-6
R-7
R-7
R-8
R-8

R-9
R-9

U
u

R-41
R-ll
T
T
T
T
T

T
T

U
U

U
T
                                 Aromatlcs
Benzene
Mesitylene
Ethylbenzene
Cunene
Xylene (m-,o-,p-)
Toluene
Styrene
2-Napthylanine
R-12(SRM 1806)
U
U
U
T-4
T-4
U
U
N
N
N
N
N
N
N
U
A-12
U
U
U
U
U
U
U
R-9. 13
u
R-13
R-13
R-13
R-9. 13
R-13
R-lA
T
U
T
T
T
T
T
T
                                  Ketones
Acetone
Methyl Ethyl Ketone
Methyl Isobutyl Ketone

Ethylene Oxide
Propylene Oxide

bis(2-Chloroethyl) Sulfide

U
T-4
T-4

T-4
T-A

u

N
N
N
Epoxldes
U
U
Sulfldes
U

U
U
U

N
N

U

R-15
R-16
R-15

R-17
R-18

u

T
T
T

T
T

u
(continued)

-------
                                                                              Section No.  3.16
                                                                              Date June 30, 1988
                                                                              Page 22
                                                                                      o
 TABLE E.  (Continued)
Selected Compounds
Methods for Direct Interface
and Tedlar Bag Samples
Gas
Cylinders
Gas
Injection
into
Tedlar Dag
Liquid
Injection
into
Tedlar Bag
Methods for Adsorption
Tube Samples
Prepare
Standard in
Desorptlon
Liquid
Prepare
Standard
on Tube
and Desorb
                                           Halogenated
Ethylidene Chloride
Ethylene Dibroialde
Ethylene Dichloride
Propylene Dichloride
1,1. 1-Trichloroe thane
Bromodichlorome thane
Chi o rod ibromome thane
Chloroform
Carbon Tetrachloride
Dichlorodif luorome thane
Methyl Bromide
Methyl Chloride
Methylene Chloride
Tetrachloroethylene
BroiBoform
Trichloroethylene
Trichlorotrifluoroe thane
Vinylidene Chloride
Ethyl Chloride
Chlorobenzene
Vinyl Chloride
l,2-Dibromo-3-chloropropane
U
T-4
R-21
T-4
R-21
U
U
R-23
R-23
U
U
U
R-21
R-21(SRM 1809)
U
R-21
R-21
T-A
U
T-4
R-30
U
N
N
N
N
N
U
U
N
N
U
U
U
N
N
N
N
N
N
N
N
A-30
N
U
N-31
A-21
U
A-21
U
U
A-23
A-23
N
N
N
A-21
A-21
V
A-21
A-21
U
U
U
N
U
R-19
R-20
R-19
R-22
R-19
U
U
R-19
R-19
R-24
R-25
R-26
R-32
R-33
R-19
R-3*
B-35
R-28
R-29
R-19
R-3&
R-37
T
T
T
T
T
U
U
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
                                                                                                           O
Rating Code
 R « Recommended.
 A « Acceptable.
 T » Theoretical.
Based on actual source test  experience  (sampling and analysis) this method
is valid and is the method of  choice among Method 18 users.

Based on actual source tests or  similar source test experience (sampling and
analysis), this method is valid.   The tester must evaluate for specific
test.

Method has no documented sampling  and analysis experience, but in theory
could be valid.
 N « Not Recommended.  Based  on  actual  source tests or similar source test experience   and/or
                      theory, this method is invalid.
 U » Unknown.
                      Method  has  no documented experience and the theoretical  aspects  are not
                      conclusive.  The tester must demonstrate that this calibration method Is
                      valid.
   The rating codes  for  calibration procedures are based on procedures specified in  applicable
sampling and/or analytical  methods.  For example, the rating code for benzene  is:  R-12(SRM  1806);
N; A-12; R-9>13!  T.   This means  that for benzene, the recommended calibration  procedure  for direct
interface and Tedlar bag samples  involves the use of gas cylinders with the procedures described
in citation 12 in Section 3.16.11 and Standard Reference Material 1806 (available  from the
National Bureau of Standards,  Galthersburg, MD); calibration standards for benzene prepared by gas
injection into Tedlar bags  is  not recommended; calibration standards prepared  by liquid  injection
into Tedlar bag*  io  acceptable following the procedures described in citation  12 in  Section
3.16.11; preparation of  calibration standards in desorption liquid is the  recommended procedure
for the adsorption tube  methods  described in citations 9 and 13 in Section 3-l6.ll;  preparation of
calibration standards on adsorption tubes followed by deaorption is theoretically valid  for use
with adsorption tube samples.
                                                                                     O
                                                           Qf**

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                                                                Section No.  3.16.1
                                                                Date June 30,  1988
                                                                Page 1
1.0  PROCUREMENT  OF  APPARATUS  AND  SUPPLIES
        For Method  18,  a number of different  sampling  and  analytical  procedures are
 considered  acceptable  for the  identification  and measurement of  the majority of
 gaseous organic  compounds emitted from industrial sources.  Persons  attempting to
 apply  these  procedures are advised to  consult  the tables presented in the Method
 Highlights Section. The  Method Highlights  Section is  intended  to provide  guidance,
 based  on current EPA methodology, for selection of the most suitable  sampling and
 analytical protocols for organic compounds of interest to  Federal,  State,  and  local
 agencies.   For  situations where  EPA methodology  is  not  applicable,  guidance for
 selection  of sampling  and analytical  protocols  based on  methodology from  other
 reputable  organizations  is  provided.    Once a suitable  sampling and analytical
 protocol  has  been selected,  then  procurement of  the  necessary apparatus and sup-
 plies  can begin.
        A  number  of the sampling and analytical methodologies covered  by  Method 18
 are common to both presurvey sampling and analysis and final sampling and  analysis.
 Presurvey sample collection  can employ either glass sampling flasks  (not employed
 for final sampling), Tedlar bags,  or adsorption tubes.  Apparatus  to determine the
 moisture  content,  temperature,  and static pressure of the  source  emissions may be
 required  during  presurvey sampling if  this information is not  available from  plant
 personnel.  Method 18  also describes several different calibration  techniques for
 use  depending   on  the  available calibration  materials  and  the  sampling and
 analytical techniques used.  Confirmation  of target compounds  in presurvey  samples
 may require  analysis by  means  other than GC alone,  such as GC/mass  spectrometry
 (GC/MS)  or GC/infrared  spectrometry  (GC/IR).  For the final sampling, in addition
 to Tedlar bags and adsorption  tubes, direct  interface sampling and dilution inter-
 face sampling are described.   Analysis of the final samples utilizes the procedures
 developed and optimized during presurvey sample  analysis.
        The descriptions  of the apparatus  and supplies  that follow apply to  items
 needed  for  both presurvey and  final  sampling and analysis, except as noted.  As
 described above, all of the following equipment  may not be required.   The  following
 procedures and descriptions are only provided as guidance  to the  tester and  are not
 requirements  of  the method.    Table  1.1  at the  end of   this section contains  a
 summary of quality assurance activities for procurement and acceptance of  apparatus
 and supplies.

 1.1 Sampling                                      '

        Guidance for the selection of a suitable  sampling technique  for a particular
 compound can be found in Table B of the Method Highlights  Section.

 1.1.1   All Sampling Procedures  -  The following  apparatus  will be  required  for all
presurvey and  final sampling procedures.   Use of alternative equipment requires
 the approval of the Administrator.

       Sampling System Check - Because of  the number  of sampling systems, volatile
organic compounds, and process operating conditions,  the  exact criteria for check-
ing the sampling system  can only  be  determined  using  the presurvey sampling data.
Upon receipt  of  all the  components  to construct  the sampling system, the  system
should be assembled and  checked over the  intended range of use (i.e., sample flow
rate,  duct temperatures).

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O
O
                                                                Section No.  3.16.1
                                                                Date June 30,  1988
                                                                Page 2

       Sampling  Probe - The sampling probe should  (1)  be  constructed  of stainless
steel, Pyrex  glass,  or Teflon tubing, (2) exhibit  an outside  diameter (OD)  of 6.4
mm,  (3) be enlarged at  the duct end to contain a glass wool plug, and (4) possess a
heating  system capable of  maintaining the sample  temperature at 0°  to  3°C above
duct  temperature.  The  expanded section of the probe must be packed with glass wool
prior to sampling.  The probe outlet must have a fitting suitable for attachment to
the  sample  line.  A  probe  approximately  1.1  m (4  ft)  long is usually sufficient;
the  exact  length can be determined during the  preliminary survey.   The selected
probe material should  be  nonreactive toward with  the  sample gas  constituents so
that  it  will  not bias  the  analysis,  as  well as appropriate to  withstand the duct
temperature.
       Upon   receiving  a  new  probe,  visually  check  it  for  adherence  to
specifications  (i.e.,  the  length  and composition  ordered).    Check  for  breaks,
cracks, and leaks.  Leak  check  the probe  and  check the probe heating system during
the  sampling  system check described above.   The probe should be able to maintain
the required temperature at the desired flow rate and remain leak free.

       Sample  Line  and Connecting Tubing - The sample  line is generally 6.4-mm OD
Teflon tubing.   Sample lines will require heat-tracing to prevent condensation of
sample constituents during sampling at some sources.   The sample temperature must
be maintained  at 0°C  to  3°C above  the  source temperature.   The capacity  of the
heating system should be  sufficient for its intended use.   Upon receipt or during
the system check, the sample line should  be checked to  ensure  that it is leak free
and will maintain the desired temperature at  the  desired  flow  rate.  It should be
noted that  heat-traced  sample  lines  require  a significant amount of electrical
current to maintain the higher temperature levels.   The electrical requirements and
the weight of  the heat-trace'd line should be  taken into account when designing the
sample train.

       Quick Connects - For connections  on  the  sample lines, gas  sampling valve,
the pump unit, cylinders, sample  bags, and calibration  gas bags,  quick connects or
the equivalent  are  needed.  When the connects come into  contact with the sample
gas,   they  should be  constructed  of stainless steel.   It  is  also useful  to have
self-sealing quick connects  on  the sampling bags.   The quick  connects can  be leak
checked during the system check.

       Barometer  -  A  mercury,  aneroid,   or  other  barometer capable  of  measuring
atmospheric pressure  to within  2.5 mm (0.1 in.) Hg may be used; however,  in many
cases the  absolute  barometric  pressure  can  be obtained from  a nearby  weather
service station.  If the elevation of the sampling point is higher than that of the
weather station,  the  reported  barometric pressure  is reduced  at a rate  of  2.5 mm
Hg/30 m (0.1 in. Hg/100 ft) of elevation difference; if the sampling point is lower
than  the weather  station,  the pressure is increased at the same  rate.   Note;   The
barometric pressure from the weather service station should not be corrected to sea
level.
       Check  the field barometer  against a  mercury-in-glass  barometer  (or  its
equival'ent).   If the  field barometer cannot be adjusted to agree with the mercury-
in-glass barometer,  it is not acceptable and should be repaired or replaced.

       Moisture  Determination  -  A moisture determination may be  required.   Two (   J
techniques  can  generally  be  used:  (1)  Method  4  or   (2)   wet  bulb/dry  bulb  >•—'
thermometers.   If Method 4 is used, the tester should refer to Section 3«3  of this
Handbook.   If  the wet bulb/dry bulb thermometers  are used,  both thermometers should

                                                         >

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                                                                Section No. 3.16.1
                                                                Date June  30,  1988
•                                                                Page 3

be  accurate  to  within  1°C.    Upon receipt,  the  thermometers  should be checked
against a mercury-in-glass thermometer to ensure that they are reading properly.

       Flow Rate  Determination - The flow  rate  in the duct may have  to  be deter-
mined  for some emission standards.   If the  flow rate  is  to be  determined,  the
tester should refer to Section 3-1 of this Handbook  and  meet the requirements and
follow the procedures of this method.

1.1.2  Glass  Sampling Flask Sampling Technique -  The following apparatus and rea-
gents will  be required for the collection of  samples (presurvey only)  using glass
sampling  flasks.     Use  of  alternative  equipment requires  the  approval of  the
Administrator.

         Purged  or  Evacuated  Glass Sampling  Flasks  -  Presurvey  samples can be
collected  in  precleaned double  ended  glass  sampling  flasks  possessing minimum
capacities  of 250  ml.    Teflon stopcocks,  without  grease,  are preferred.   Upon
receipt, flasks should be checked  to ensure that they are not broken.  Flasks must
be cleaned prior to  use.  The cleaning procedures are described later in Subsection
3.2.  If the  flasks  do not meet these requirements, replace or reclean.

1.1.3  Tedlar Bag/Evacuated  Container  and Adsorption Tube Sampling - The  following
apparatus will be  required  for the collection of  presurvey  or final samples using
adsorption tubes or Tedlar  bags housed in evacuable  containers.   If the  apparatus
are purchased separately, each  item should be  checked  individually  as   described
below.  Following this, all components should be assembled, as they will be used in
the field and then checked using the following procedures:
       1.   Assemble the sample train as described in Subsection 4.3-1.
       2.   Leak check the train as described in Subsection 4.3.1.
       3.   Attach  a primary gas  test  meter to the inlet  of the sample train and
            pull the desired flow  rate  through the sample train for the typical
            sample run time.  The  measured  volume  should  be  within 10% of the
            calculated volume or rate.   If  the system does not meet these
            requirements, replace or repair and then recalibrate.

       Tedlar  Bags   (For Sampling  and  to  Prepare  Gaseous Calibration  Standards)-
Bags used to  collect field  samples and prepare gaseous calibration standards must
be constructed of a  suitable material, be leak free,  and  have the proper fittings.
Typically,  self-sealing quick disconnects are  used on the sample bags.   Tedlar is
the material  of  choice for  the  sample bags,  however other materials may be used
successfully.   If the sample bags are constructed by the tester, they are generally
double-sealed.  The  exact bags to  be used in the  field test  or for making calibra-
tion standards must pass three criteria as follows:
       1.    Bags  must pass the leak check as described in Subsection 4.3-1.
       2.    The organic components  that  are to be collected in  the  bags  should be
            placed in a  bag  at about the  same concentration for which it will be
            used,  and the organic  concentration in  the bag determined as soon as
            possible after this.  The organics should then remain  in the  bag  for a
            period  equal  to  the   time  anticipated  between  field  sampling  and
            analysis.  The  concentration, upon reanalysis,  must be within 10% of
            the original concentration.
       3.    Next,  the bag should be emptied and refilled with zero air or  nitrogen.
            It should be  allowed to  sit  for,  at  least  2  hours  and  then  be
            reanalyzed;  the  concentration of  the organic(s)  in the  bag must  be

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                                                                Section No. 3-16.1
                                                                Date June  30,  1988
                                                                Page 4

            less than 10% of the original concentration.
 If  the bags do not pass the leak checkt they must be reconstructed.  If they do not
 pass  the second  and third  criteria,  a  different material  of construction  or  a
 different sampling technique must  be used.   If the bags do not meet these require-
 ments, replace, use an alternative technique or use a different sampling technique.

       Rigid  Leak-Proof Container  -  Rigid  leak-proof containers  must be  of the
 proper size to fit the  bags  and are generally made of rigid plastic.  However, the
 material  of  construction is typically not  important since  the container  does not
 come  into contact with  the  sample gas.   Containers usually have a  clear  top or
 window in them to check that the bag1 does not overfill during testing.  The top of
 the container must have connections to attach the  sample  probe to the outside and
 the sample  bag  to  the  inside.   A connection  for the sample pump  must  also be
 available  on  the container.    Upon  receipt or  construction  of  the container,
 assemble  the system  as  it will be used in the field  and  then leak check it at the
 maximum vacuum anticipated.   Inflate a bag  to the  degree  it will be  filled in the
 field  and check  that  the bag  can be removed  after it  has been  filled  to  allow
 external  heating.   If  the bag system is designed  to keep  the bag at a specified
 temperature,  then  the  heating  system   must be  checked  as  described  below in
 Subsection  1.1.6.   If  the  container does  not  meet  these  requirements, modify,
 repair, or replace it.

       Pump - For the indirect sampling  technique  (pump  after the bag or charcoal
 tube), any pump  of proper capacity can be used.   If the  pump  is  to be used  for a
 direct sampling  technique {pump  in the  sample  line),  the pump  internals must be
 leakless  and made of stainless steel or, preferably,  Teflon.  Upon receipt,  check
 for proper specifications.  If  the pump does not meet the  specifications, repair or
 replace it.

       Flowmeter  -  The  flowmeter must be  of  the  proper  flow rate  range.    Upon
 receipt,  check  the specifications  and then  calibrate as  described in Subsection
 2.1.3.  If the flowmeter does not meet the requirements, replace or recalibrate it.

       Adsorption Tube  -  An  absorption tube must  (1)  be  of adequate  capacity, (2)
 contain the proper adsorption  material, and  (3)  consist of a primary  and secondary
 section.  The  selection of  the proper  type  and size of  adsorption tube should be
 based on  previous experience  (including  the literature and  tables in the  Method
 Highlights)   or  laboratory  evaluation.    The  selection and/or evaluation  of the
 proper adsorption  tube is  described in  detail  in Subsection 3.4.   The  criteria
 shown in Subsection 3'4 must be met or the tubes must be replaced or modified.

       Personnel  Sampling Pump  -  -A  personnel  sampling  pump  can  be used for
 collecting adsorbent  tube simples.   It  must sample  at  or  be adjustable  to the
 proper flow rate  range.  Upon  receipt,  check the specifications  and  calibrate as
 described in Subsection 2.1.4.  If  it does not meet the specifications, replace or
 calibrate it.

 1.1.4  Direct  Pump Sampling  Procedure  - The  direct  pump  sampling procedure  will
 require the same apparatus described  in  Section 1.1.3  for bag and adsorption tube   ^^^
 sampling.   The only  difference is  that the  pump internals must be constructed of  (]
materials that will not interfere in the  analysis (i.e., Teflon or stainless steel)  \	J
 and the  rigid container  does  not  have   to  be  leak  free.   The system should be
assembled, leak checked and then the flow rate checked  as  described above.   If the
o

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                                                                Section No. 3-16.1
                                                                Date  June 30, 1988
                                                                Page  5

 system does not meet  the  criteria,  then it must be  replaced  or  repaired and then
 leak checked and recalibrated.

 1.1.5  Explosion Eisk  Bag  Sampling Procedure - The following apparatus, in addition
 to the apparatus described in Subsection 1.1.3,  will be required for collection of
 bag samples in areas where there  is  any possibility of explosion.  These procedures
 assume that the sample gas collected is not above the lower explosive limit.  If it
 is,  a  complete safety  plan should be developed  and  reviewed  by  the  plant and
 tester.   This Handbook will not attempt to describe the procedures used to collect
 explosive gases.
   The major concern in most areas  having  an  explosion potential  is that no open
 flames or non-intrinsically safe  electrical equipment be used.  The  first approach
 to sampling in these areas is  to remove  the electrial  systems (i.e., pumps) to an
 area that is not explosive.   This can be accomplished by  running the vacuum line
 from an  area that is  not explosive  to the  sample bag or  charcoal tube  in the
 explosive area.  The vacuum line  can be run up to 200 to 300 feet with no problems.
 Sampling is then conducted in the normal manner.
        Another approach described in Method 18 uses a steel canister  to provide the
 vacuum source.  This  approach  is difficult and can  still  be  hazardous because it
 involves handling a steel  container,  and possibly a stainless steel probe, in an
 explosive area.  Another alternative is the use of an intrinsically safe pump, such
 as a  personnel sampling  pump,  with  adsorption tubes  or Tedlar bags  housed in
 evacuable  containers.    Any  system  that  is  purchased  or  constructed must  be
 leakless,  be  able  to  control  the flow rate  properly,  and meet  all plant  safety
 requirements.

 1.1.6  Heated  Bag  Sampling Procedure - This  procedure  must be used in the event
 that condensation is observed  in the  bag and/or sample line  during testing or if
 the  sample bag retains  more than  10% of the sample concentration based on the post-
 test sample bag retention check.   The  apparatus  described  below will be required,
 in addition to the apparatus described in Subsection 1.1.3-   Both the sample line
 and  container must  be  heated to maintain the bag at a specified temperature  (i.e.,
 0°C  to 3°C above source temperature).  The sampling system is checked in the  manner
 described above, except  that  the heating  system must  also be  considered; check
 procedures should consider use  of the  system at  ambient temperatures less than the
 laboratory temperature (including wind chill factors).  The entire surface of the
 sample  probe and the  sample  bag  must  be maintained  at  the specified temperature.
 A  possible alternative to  maintaining the bag at the specified  temperature is the
 addition  of external heating with heat lamps prior  to analysis.   The exact  system
 that  will be suitable  for any given source should be determined  prior to testing,
 if possible.   The operation and checks  of heated sampling systems are described in
 Subsection 4.3-   If the system  does  not meet all  the  criteria, use  a different
 approach  or repair the system and recalibrate.

       Heated  Bag Sample  Container -  The  heated  bag  sample  container must  be
 capable  of  maintaining the  entire  bag at  the  specified  temperature.     If  an
 electrical  source is used  to heat the  container,  the tester must be aware  of the
 additional  explosion potential  that is  created.   One check on  the  system  can  be
made with  a thermocouple in the sample cavity; this check of  the  system will not,
however,   demonstrate   that all   the  surfaces  are  maintained  at  the  required
 temperature.  All external  surfaces  of the  container should be well  insulated.   A
visual check of  the system should reveal if the system appears to  be sufficiently
insulated.   If the system allows the  bag  to have  cooler  surfaces, the  posttest


                                                  7

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                                                                Section No.  3.16.1
                                                                Date June 30,  1988
                                                                Page 6
retention check on the bag will probably fail.
                                                                                     o
       Heated Sample  Lines  and Probe - The sample probe and  sample  line must also
be capable of maintaining the specified temperature.   They should also not have any
cooler surfaces.   These can  be checked by pulling  the desired flow  rate through
them  and  then  checking   the  temperature  in  the  line  and/or  probe  with  a
thermocouple.    Proper  insulation  is necessary  to maintain  the  temperature
throughout the entire length.   If  the temperature cannot be maintained, replace or
repair the line and/or probe and then recheck.

1.1.7  Prefilled  Tedlar  Bag Sampling Procedure - This  procedure is  an alternative '
to the  heated bag  sampling procedure.  The  following apparatus and  reagents are
required for this procedure,  in addition to the apparatus  described in Subsections
1.1.3  and  1.1.4.    The  prefilled  bag sampling system  is  used  to dilute  the
concentration of  the  condensibles  below saturation.   This  system  can  also be used
to dilute  the gases  to below the  lower  explosive  limit.   The  major difference
between  the  prefilled bag  sampling system and the  other  bag sampling systems is
that  the volume  of diluent  gas  added to  the sample  bag and  the  volume of - gas
sampled  must  be  accurately measured.   The dilution must  be accounted  for in the
calculation of the  measured gas concentration.  Therefore,  the diluent gas must be
added with a  calibrated dry  gas  meter or a  calibrated  flowmeter;  then,  during
sample collection,  the gas  collected must  be  accurately measured using a flowmeter
or a  metered pump.   To  obtain the  required  accuracy,  the flowmeter  and  pump are
placed in  the  sample  line  prior to  the sample  bag.  Since condensation may occur,
the flowmeter  and pump must be housed in a heated box.  This system is checked in
the same manner  as a dilution system  (see Subsection  1.1.9).   The check for the
prefilled system is described in Subsection 4.3-4.

       Heated Flowmeter  -  A calibrated heated  flowmeter is  required to accurately
determine  the  volume  of gas  sampled.   The flowmeter should be housed in  a heated
box  that  will maintain  the  specified  temperature.    The  flowmeter should  be
calibrated as  described  above in Subsection  2.1.3.   If the  criteria  are  not met,
replace  or repair  and  then  recalibrate.   A metering type pump may be used to
replace  the flow rate meter and the pump.

       Positive Displacement Teflon-Lined Pump - A positive displacement pump lined
with Teflon or constructed  of stainless steel,  of proper capacity  and contained in
a heated box is  required.   A Teflon-coated diaphram-type pump  that can withstand
120°C and  delivers  1.5 liters/minute  is typically used.   Upon  receipt,  check the
pump  for capacity and then conduct a  leak check on the  pump.   The  pump must be
leak  free  at  all  vacuum settings.   The heating system will be  checked during the
sampling system check.   If the pump is not  of the  correct capacity  and  not leak
free,  then replace or repair it.

       Heated Box for Flowmeter and Pump -  The flowmeter and pump must be contained
in a  heated  box  to maintain  the proper temperature.   Construct the box such that
the temperature can be  controlled  and monitored.   After  construction, check the
system to ensure that it will  maintain the  desired temperature(s).   If it  will not
maintain the temperature(s), repair the unit.

1.1.8   Direct  Interface  Sampling Procedure -  A heated probe, heated  sample  line,
heated gas  sampling valve, needle  valve,  and  charcoal adsorber are  required for
direct interface sampling.  The required  apparatus and reagents pertaining to the
                                                                                      O

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                                                                Section No. 3.16.1
                                                                Date  June  30, 1988
                                                                Page 7

gas  chromatograph are  described below  in Subsection  1.2.   After  the individual
components  are checked as shown  below,  the sampling system  should  be assembed as
shown in Subsection 4.3.6 and checked using the following procedures:
       1.   Turn  on  the heating  system and adjust  to the maximum  temperature at
            which it is to be used.
       2.   Connect the inlet to  the sampling  probe.   After the heating system has
            stabilized  at  the temperature  setting,  turn on  the  pump and evacuate
            to about 10 in.  of H20.  The  system must  be leak free;  no flow should
            be observed from the charcoal  adsorber  system.   If  the  system  is not
            leak free, repair the system.
       3.   After  the  system has 'been  shown  to  be leak  free,  adjust  the  needle
            valve until the  flow rate that will be used in  the field is obtained.
            The temperature  at  the discharge of the heated  sample valve should be
            at the  set temperature.  Insert a thermocouple  into the  inlet  of the
            probe to insure  that the first several feet of  the probe and line are
            properly heated.   If the set  temperature  is not obtained,  repair the
            system or  use  the  temperature obtained  for a  recalibration of the
            temperature setting.

       Heated  Probe  and Sample Lines  - The. sample  probe  and  sample  line must be
equipped with  a heating system  and insulation.  All of the  interior surfaces must
be maintained  at  the  temperature setting.   Although all  the  interior surfaces can
not be easily  checked,  installing proper insulation  and following the system check
shown above should be sufficient  to determine  the  adequacy  of the probe and sample
line heating system.

       Heated  Gas  Sampling  Valve - A  heated  sampling valve  (which  includes the
sample  loops)  is  required  to  maintain the  sample injected into  the  GC at the
desired temperature.  The  sample valve and loop are generally  enclosed  in an oven
in which the temperature can be  controlled and monitored.   Upon receipt, check the
temperature controller.

       Charcoal Adsorber - The charcoal adsorber is required to remove the organics
from the excess flow.through the  system.   Since  the  charcoal adsorber is used only
for tester  safety, there  are no requirements on the adsorber.   However, since the
charcoal  will  be  spent  with  time, the  tester  should change it  periodically.
Alternatively,  the flow can be vented at a safe distance away from any personnel.

1.1.9  Dilution  Interface Sampling  Procedure  -  In addition  to the  apparatus des-
cribed in Subsection  1.1.8,  dilution pumps, flowmeters and valves  which  are con-
tained in a heated box,  and diluent gases  are required for  the dilution interface
system.    The  calibration of the dilution  system  is described  in  Subsection 2.2.
The individual components should  be checked  as  shown below and then  the  system
should be calibrated as described in Subsection 2.2.   If the system does  not meet
the calibration requirements, it should be replaced,  or repaired and recalibrated.

       Dilution Pumps  - Two Model  A-150 Komhyr Teflon positive displacement-type
pumps,  or  equivalent models capable of delivering 150  cc/minute,  are required.
Alternatively,  calibrated flowmeters can be used in  conjunction with Teflon-coated
diaphram  pumps.    Upon  receipt  calibrate the  pumps,  or  flowiaeter  and  pump  as
described   in  Subsection  2.1.     If   the "pumps  do   not  meet  the calibration
requirements,  replace or repair and then recalibrate.

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                                                                Section No. 3-16.1
                                                                Date June  30,  1988
                                                                Page 8

       Floimeters  -  Two flowmeters are  required  to measure the diluent gas,  at a
 rate of about 1350 cc/minute.  Upon receipt, the flowmeters should be calibrated as
 described  in Subsection 2.1.    If the  flowmeters  do  not  meet  the  calibration
 critera, replace or repair and then recalibrate.


       Diluent  Gas  -  Diluent gas in cylinders  fitted with regulators  are required
 for sample dilution.  Nitrogen or hydrocarbon-free air can be used depending on the
 nature of  the source  gases.   Alternatively,  ambient air  can be cleaned and dried
 with charcoal and  silica gel.  The organics in the  dilutent  gas must  be below the
 detection limit.

       Heated Box for Sample Dilution System - The pumps and control valves must be
 housed in a heated box  to  control and  monitor the temperature.  After construction
 or receipt, check  the temperature control system.   If the box cannot  maintain the
 desired temperature, replace or repair and recheck.

 1.2  Sample Analysis

       The analysis of  Method 18 samples  requires the use of a gas chromatograph
 (GC)  regardless of  the technique  used for  either  presurvey or  final  sampling.
 Guidance for the selection of suitable GC detectors  is provided in Table  C in the
 Method Highlights Section.   As a starting point for the analysis of the presurvey
 sample.  Table  D  in  the  Method  Highlights  Section provides  guidance  for  the
 selection of a  suitable packed GC column.   Any interferences  with the GC analysis
 may be source-specific,  so the most suitable  analytical  system must be established
 using the presurvey samples.   The following apparatus will be required for the GC
 analysis.

 1.2.1  Gas Chromatograph - A GC equipped with  a  suitable  detector as  specified in
Table  C  in  the Method Highlights  Section.    The  GC shall  be  equipped with  a
 temperature-controlled  sample loop  and valve assembly for  analysis  of gas samples
or a  temperature-controlled  injection port  for  analysis  of liquid  samples  from
 adsorption tubes.  Use  of  alternative techniques  for introducing samples  into the
GC requires the approval of the Administrator.   The GC should  be equipped with a
 temperature-controlled  oven,  while  a  temperature-programmable oven  may  also  be
 required for some  analyzers.  Method  18 may be  used to  quantify gaseous organic
 compounds at  concentrations  ranging from  about  1  part-per-million (pptn)  to  the
upper  range  governed   by  detector  saturation  or  column  overloading.   For  the
combination of  GC  options  chosen,  the  lower  limit of quantitation, as defined by
Knoll'12,  for the  target organic compounds  should be less  than  the emission limit
 for the particular source being tested.

 1.2.2   GC Column  -  Guidance  for the  selection  of  the  appropriate GC column is
provided in  Table D  in  the Method  Highlights Section.   The  columns listed  in
Appendix I to Table D  have  been found  to  work for  analysis  of the corresponding
organic compounds  under certain  conditions.   Since interfering  compounds  may be
 source-specific. Method 18 permits the use of any GC column, provided the following
precision and accuracy are achieved:

    Precision:  Duplicate analyses within 5 percent of their mean value.
    Accuracy:   Analysis results of  an  audit sample within  10  percent of the
              prepared value.
o
o

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                                                                Section No. 3.16.1
                                                                Date June  30,  1988
                                                                Page 9


 In  addition,  resolution of  interfering compounds from target  compounds  should be
 achieved.   For determining whether acceptable resolution has been achieved, follow
 the procedures  described  in Appendix C "Quality Assurance Procedures", Procedure 1
 "Determination  of Adequate Chromatographic Peak Resolution."*3

 1.2.3   Recorder  -  A  linear strip  chart  recorder is  required,  as a minimum,  to
 record  the GC  detector output.   Alternatively,  an  electronic integrator  may be
 used and is generally  recommended.

 1.2.4   Recorder  or Electronic  Integrator Paper -  Consult operator's manual  or
 manufacturer for correct type.

 1.2.5   Regulators - Gas  cylinder regulators will be required for use of the gas
 cylinders described in Subsections 1.3.1, 1.3-2, and 1.3«3«  Consult with suppliers
 of gas cylinders to determine the proper type of regulator required.

 1.2.6   Tubing and Fittings  - Tubing and fittings will be  required to connect the
 gas cylinder regulators to the GC.

 1.3  Reagents and Glassware

       The  exact  reagents  and glassware required  depend  on the sampling procedure
 chosen, the calibration techniques to be used,  and  the particular requirements of
 the GC system.

 1.3.1   GC Carrier Gas -  The carrier  gas  selected must be  hydrocarbon-free.   The
 type of carrier gas depends on the  type of GC detector  and GC column being used.
 Consult  the  GC  operator's manual,   the GC  manufacturer,  and/or  the  column
 manufacturer for recommendations on  the optimum carrier gas  for a particular appli-
 cation .

 1.3.2  Auxiliary  GC Gases - Certain GC  detectors  will require auxiliary gases for
 proper operation.   Consult  the GC  operator's manual  or the GC  manufacturer for
 recommendations on a particular application.

 1.3.3    Calibration   Gases  -  These   include  cylinder  gases  containing  known
 concentrations  of  target  organic  compounds  for  preparation  of GC calibration
 standards,  direct  use as  GC calibration standards,  or calibration of a  dilution
 interface system.  If  gases are not available in the required concentrations for GC
 calibration,  procure   the  reagents  and  glassware described in Subsections  1.3.4
 through 1.3.7.

 1.3.4   Zero Gas -  Hydrocarbon-free air or nitrogen, for preparing gaseous  cali-
 bration standards from calibration gas cylinders or liquid organic compounds.

 1.3.5  Liquid Organic Compounds - Pure or high purity liquid (occasionally gaseous)
 samples of all the organics for which calibration standards will be prepared.

 1.3.6  Syringes - Calibrated, gas  tight 500-,  10-,  and  1.0-microliter sizes  with
maximum  accuracy,  for  preparing  gaseous  calibration  standards,  for  preparing
 adsorption tube standards,  and  for injection of liquid standards  and  samples  into
 the GC.   Other size gas tight syringes may be appropriate.

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                                                                Section No. 3.16.1
                                                                Date June  30,  1988
                                                                Page 10


1.3.7  Midget Impinger/Hot Plate Assembly -  To prepare gaseous standards In Tedlar
bags  from liquid  organic compounds  requires  a  midget impinger  equipped with  a
septum and a tee on  the  inlet stem and a boiling water bath on a hot plate.  A dry
gas meter, previously described in Subsection 1.1.1, is also required.

1.3-8  Screw  Top Septum. Vials  -  For preparation of adsorption  tube standards and
samples,   7-ial amber screw top septum vials with Teflon-lined septa are required.

1.3-9   Desorption Liquid  -  For preparation  of  adsorption tube  standards  and
samples,  desorption  liquid is required.  For the correct  desorption liquid,  refer
to the appropriate NIOSH method for the target compound(s)  referenced in Table B in
the Method Highlights Section.
o
                                                                                       o
                                                                                        o

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                                                                Section No. 3.16.1
                                                                Date June 30, 1988
                                                                Page 11

       Table 1.1.    ACTIVITY MATRIX FOR PROCUREMENT OF APPARATUS AND SUPPLIES

Apparatus
All Sampling
Procedures
Sampling system
check
Sampling probe
Sample line and
connecting tubing
Quick connects
Barometer
Moisture
determination
Flow rate
determination
Glass Sampling
Flask Technique
Purged or evacu-
ated sampling
flasks

Acceptance limits
Maintain proper
flow rate and
temperature
Proper material
of construction
and capable of
maintaining proper
temperature
Constructed of
Teflon and capable
of maintaining
proper temperature
Stainless steel
construction and
leak free
Capable of measuring
atmospheric pressure
to within 2.5 mm
(0.1 in.) Hg
See Section 3-3 of
this Handbook
See Section 3.1 of
this Handbook
Double ended glass
flask with Teflon
stopcocks
• • •
Frequency and method
of measurement
Upon receipt, conduct
check in specified
subsection
Visually check and
then run heating
system checkout
Visually check and
then run heating
system checkout
Visually check and
conduct leak check
Check against mercury
in-glass barometer or
equivalent
(Sec. 3-5-2)
Same as in Section 3-3
Same as in Section 3-1
Visually check upon
receipt

Action if
requirements
are not met
Repair or return
to manufacturer
Repair or return
to manufacturer
Repair or return
to manufacturer
Repair or return
to manufacturer
Determine cor-
rection factor,
or reject
Same as Sec. 3-3
Same as Sec. 3«1
Return to
manufacturer
(Continued)

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                                                                Section No. 3-16.1
                                                                Date June 30, 1988
                                                                Page 12
                                                                  o
Table 1.1  (Continued)
Apparatus
Evacuated Con-
tainer and Adsorp-
tion Tube
Sampling

Tedlar bag
 Acceptance limits
Constructed of
material in which
organics remain
stable and are not
retained; leak free
Frequency and method
   of measurement
Upon receipt, leak
check and conduct
stability and
retention check
Action if
requirements
are not met
 Return to man-
 facturer, change
 material, or
 use different
 sampling tech-
 nique
Rigid leak-
proof container
Leak free and
of proper size
Upon receipt,
visually check and
then conduct leak
check
 Repair or return
 manufacturer
O
Pump
Leak free and of
proper capacity
Visually check and
then conduct leak
check and flow rate
check
 Repair or return
 to manufacturer
Flowmeter
Proper flow rate
range and cali-
brated
Upon receipt, check
specifications,  check
visually,  then
calibrate
 Return to manu-
 facturer or
 repair and then
 recalibrate
Adsorption
tube
Proper material,
adequate capacity,
and consisting of a
primary and second-
ary section
Conduct laboratory
evaluation or consult
literature
 Replace or make
 modification and
 recheck
Personnel sampling
pump
(Continued)
Proper flow rate
range and calibrated
Upon receipt, check
specifications, then
calibrate
 Return to manu-
 facturer or
 repair and then
 recalibrate
                                                                  O

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                                                                Section No. 3.16.1
                                                                Date June 30, 1988
                                                                Page 13
Table  1.1   (Continued)
Apparatus
Direct Pump
Sampling

Pump
Flowmeter
Explosion Risk
Bag Sampling

Nonexplosive
vacuum source
Heated Bag
Sampling

Sampling bag
Heated bag
container
Heated sample
lines and probe
Prefilled
Bag Sampling

Heated flowmeter
(Continued)
 Acceptance limits
Stainless steel or
Teflon-lined, proper
capacity, leak free,
and heated
Proper flow rate
range, leak free,
and heated
Proper flow rate
capacity and
intrinsically safe
 Same as above
 Leak free,  adequate
 capacity,  and
 heat system
 capable of main-
 taining proper
 temperature
 Constructed of
 Teflon and/or
 stainless steel
 Same as  above
Frequency and method
   of measurement
Visually check, then
conduct leak check,
flow rate check, and
system heating check
Visually check, then
conduct leak check,
flow rate check, and
heating check
Check with plant
safety rules and
check flow rate
capacity
 Same as above
 Visually check,
 then conduct
 leak check and
 heating check
  Visually check,
  then conduct
  heating check
  Same  as  above
Action if
requirements
are not met
 Return to manu-
 facturer or
 repair and
 recalibrate
 Return to manu-
 facturer or
 repair and
 recalibrate
 Return to manu-
 facturer or
 repair and
 recheck
  Same as above
  Return to manu-
  facturer or
  repair and
  recheck
  Return to manu-
  facturer or
  repair and
  recheck
  Same  as  above

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                                                                Section No. 3.16.1
                                                                Date June 30, 1988
                                                                Page 14
Table 1.1  (Continued)
o

Apparatus
Stainless steel or
Teflon-lined pump
Heated box for
flowmeter and
pump
Direct
Interface
Sampling
Heated probe, pump
and sample
lines
Heated GC sample
valve
Dilution
Interface
Sampling
Stainless steel or
Teflon-lined pump
Dilution pump
Flowmeters
Diluent gas

Acceptance limits
Same as above
Proper flow rate
range and capacity;
heating system
capable of main-
taining the proper
temperature
Same as above
Proper valve and
heating system;
consult owner's
manual
Same as above
Teflon-lined
metering pump
with capacity
of 150 cc/min
Proper flow rate
range and
calibrated
Hyrocarbon-free
air, nitrogen, or
dry cleaned air

Frequency and method
of measurement
Same as above
Visually check,
then conduct
leak check, flow
rate check, and
heating check
Same as above
Visually check,
then conduct
check of heating
Same as above
Visually check,
then calibrate
Visually check,
then calibrate
Visually check cylin-
der; check cylinder
pressure; run a blank
to monitor impurities

Action if
requirements
are not met
Same as above
Return to manu-
facturer or
repair and
recheck
Same as above
Return to manu-
facturer or
repair and
recheck
Same as above
Return to manu-
facturer or
repair and
recalibrate
Return to manu-
facturer or
repair and
recalibrate
Return to
manufacturer
                                                                                       O
(Continued)
                                                                                       o

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                                                                Section No. 3.16.1
                                                                Date June 30, 1988
                                                                Page 15
Table 1.1   (Continued)
Apparatus
Heated box for
sample dilution
system
Sample Analysis

Gas chromatograph
GC column
Strip chart re-
corder or elec-
tronic integrator
Regulators
Reagents and
Glassware

GC carrier gas
Auxiliary gas
Calibration gas
(Continued)
 Acceptance limits
 Heating system with
 temperature con-
 troller and monitor
 Suitable detector,
 precision of +_ 5#t
 and accuracy of
 + 10%
Adequate peak
resolution
See owner's manual
Proper CGA fittings
and pressure
control
As specified by GC
owners manual and
hydrocarbon-free
As specified by
owners manual
Proper compounds
and known concen-
tration in proper
range
Frequency and method
   of measurement
Conduct heating
check
Refer to Table C
in Method Highlights
then check GC with
applicable organics
 Upon receipt, use
 procedure described
 in 40 CFR 60, App. C
 or Method 625
 Upon receipt, check
 as recommended by
 manufacturer
 Upon receipt, attach
 to cylinder and leak
 check
 Visually check upon
 receipt; check.cyl-
 inder pressure
 Visually check upon
 receipt; check cyl-
 inder pressure
 Upon receipt, check
 cylinder tag and
 certification; check
 cylinder pressure
Action if
requirements
are not met
Return to manu-
facturer or
repair and
recheck
Return to manu-
facturer or
repair and
recheck
Return to manu-
facturer or
change con-
ditions and
recheck
Repair or
return to
manufacturer
Return to manu-
facturer or
repair or
replace fitting
and recheck
Return to
manufacturer
Return to
manufacturer
Return to manu-
facturer or
remake or rename

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                                                                Section No. 3.16.1
                                                                Date June 30, 1988
                                                                Page 16
o
Table 1.1  (Continued)

Apparatus
Zero gas

Acceptance limits
Hydrocarbon-free
air or nitrogen

Frequency and method
of measurement
Visually 'check upon
receipt; check cyl-
inder pressure ,

Action if
requirements
are not met
Return to
manufacturer
                                                                                    O
                                                                                     o

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                                                              Section No.  3.16.2
                                                              Date June 30,  1988
                                                              Page  1
 2.0    CALIBRATION  OF  APPARATUS

       Calibration  of the  apparatus is  one  of  the most  important functions  in
maintaining data quality.    The  detailed calibration procedures  included in  this
section  were  designed for  the sampling equipment specified in Method  18 and de-
scribed  in  the previous section.  The  calibration  of the analytical equipment  is
described  in   the  section  detailing the  analytical procedures,  Section 3-16.5.
Table 2.1 at the end of this section summarizes the  quality assurance functions for
the calibrations addressed in this section.  All calibrations including  the analyt-
ical equipment should be recorded on standardized forms  and retained in  a calibrat-
ion log book.

2.1  Metering Systems

2.1.1  Met  Test  MeteT - The wet  test meter must be calibrated and  have  the  proper
capacity.   For Method  18,  the wet  test  meter should have a  capacity  of about  1
L/min.  No upper limit  is  placed on  the capacity; however,  the wet  test  meter  dial
should make at least one complete revolution at the  specified flow rate  for each  of
the three independent calibrations.
       Wet test meters are  calibrated by  the manufacturers to an  accuracy of ± 2%.
Calibration of the  wet test meter must be  checked  upon receipt  and  yearly  there-
after.  A liquid positive  displacement  technique can be used to verify  and adjust,
if necessary,  the accuracy of the wet  test meter to  +_  2%.  This technique  is de-
scribed in Sections 3-5.2,  3.8.2, and 3.15.2 of the  Handbook.

2.1.2  Dry  Gas Meter -  A  dry gas meter  is required  for  gas  and liquid  injection
calibrations,  to prefill bags prior to sampling using  the prefilled bag dilution
technique, and/or to  calibrate the flow rate meters.   For Method 18, the dry gas
meter is the same size or  smaller than  the  dry  gas  meter  typically  used  for  Method
6.  The  meter must have an accuracy of +_ 3% for the flow rate  and  sample  volume
used.  Calibration  of the  dry gas meter must  be conducted initially  upon receipt,
quarterly when  utilized to  make laboratory calibration  standards, and  following
each field test series for  field  use.   The  calibration procedures are described  in
Section 3.5.2 of this Handbook.

2.1.3  Flow Rate Meter(s)  - Flow rate  meters are needed  for  (1)  sampling and (2)
making calibration standards.  Since  they are  used  to determine  flow rate and for
total volume determinations, the  flow rate meter(s)  selected must have an accuracy
of +_  3%  for  the  flow  rate  and  total sample  volume  for which  they  are  used.
Acceptable  flow rate  meters  include rotameters,  critical  orifices,   mass
flowmeters,  and dry gas meters.   If  data from  the flow  rate meter is used only as
an indicator of the flow rate and is not used in any of the emission  calculations,
then the accuracy of  +_  3%  does not apply.   While it is  desirable to  calibrate the
gas flowmeter  with  the cylinder gas to be measured,  the quantity available and cost
may preclude it.   The error introduced  by using the diluent gas for calibration in
place of the actual gas  to be  measured  is insignificant for gas  mixtures of up to
1,000 to  2,000 ppm.

       Initial Calibration  -  The flow  metering system  should be calibrated when
first  purchased  and  at  any time  the  posttest  calibration yields  a calibration
factor that  does  not  agree within  5%  of  the  pretest  calibration  factor.    A


                                             (//(*

-------
                                                              Section No. 3.16.2
                                                              Date June 30, 1988
                                                              Page  2


calibrated  wet test meter,  calibrated dry gas  meter,  or a  properly sized bubble
meter should be used to calibrate the metering system.
     The  flow  rate meter should be calibrated in the  following manner before its
initial use in the field.
     1.   Leak  check the flow rate meter and pump as follows:
          a.  Temporarily  attach a suitable rotameter (e.g.,  0-40 cm3/min)  to
             the outlet of  flow rate system.   The pump should be placed either
             before or  after the flow rate meter based on where it will be used.
             Place a vacuum gauge at the inlet to the drying  tube.
          b.   Plug the  flow rate system  inlet.   Evacuate to a  pressure  at least
             equal to the lowest pressure  that will be encountered during use.  If
             the  system usually operates  at  or near atmospheric conditions, then
             pull a  vacuum of  25 mm (1 in.) Hg.
          c.  Note the flow rate as indicated by the rotameter.
          d.  A leak  of  £0.02 L/min must be recorded or leaks >  0.02 L/min must be
             eliminated.
     2.   Attach  the  wet test meter, bubble meter,  or  calibrated dry gas  meter to
          the inlet of the flow  rate metering system.
     3.   Run the pump for 15 minutes with the flow rate set at the midrange flow to
          allow the pump to  warm up  and to  permit the interior surface of the wet
          test  meter to become wet.
     4.   Collect  the information  required in the  forms provided  {Figure  2.1A
          (English units) or  2.IB  (metric units)  when calibrating a dry gas meter ,
          rotameter,  or  mass flow meter,  and Figure  2.2A (English units)  or 2.2B
          (metric units) when calibrating a critical orifice} using sample volumes
          equivalent  to  at  least  five revolutions  of  the dry  test meter.   Three
          independent runs must  be made.
          a.  For critical orifices,  runs will  be conducted at the single flow rate
             of the orifice meter.   The runs should  be  at three different vacuums
             that are greater than  one half an atmosphere (i.e.,  18,  19 and 20 in.
             Hg.).  This is  to  demonstrate that  the  orifice  yields the same
             flowrate at all critical vacuums.
         b.  For rotameters, mass flow meters,  and  dry  gas meters, runs will be
             conducted at three different flow rates over the range to be used
             (top, middle, and bottom of range).
      5. Calculate the  Yx  for each run for the dry gas  meter,  rotameter  and mass
         flowmeter or calculate the K'  for  the critical orifice as shown  on the
         data  forms.    Adjust  and  recalibrate  or reject the dry  gas  meter,
         rotameter, or mass flow meter if one or more values of Yj fall outside the
         interval Y +_ 0.03Y, where Y is the average for three runs.  Otherwise, the
         Y  (calibration factor)  is  acceptable  and is to  be  used  for  future checks
         and subsequent test runs.   The  K'  should be within  3#  of the average for
         all three runs.   If this  is  not true, reject the orifice  or  repeat the
         calibration until  acceptable results  are  obtained.   The completed  form
         should be forwarded to the  supervisor for approval,  and then filed in the
         calibration log book.

     Posttest Calibration Check - After each field  test series,  conduct a calibra-
tion check as  described above in Subsection 2.1  concerning the  initial calibration
with the following exceptions:
o
 o
 o

-------
         // /ftfl   Calibrated by   AT ^      Meter system no.
                                       in. Hg   Ambient temperature
Barometric pressure, Pa =

Type of primary meter:  wet test

Type of flowmeter calibrated:   rotameter    X  i  dry gas meter
                                                                     -fC>  Primary meter no.
                                          , dry gas
     ,  or bubble meter
                                                                      , or mass flowmeter
Primary meter readings
Initial
reading
(\J \ a
*pi ' •
ft3
0
0
O
Final
reading
I\J \ a
\vpf I •
ft3
0.10(*(,
O.lObb
/• 00-04
Initial
temp,°F
(tpi)
oF
tf
90
•9-0
Final
temp,°F
(tpf)
oF
CffCj
W
9-ft
Press
drop
(Dp) =
in.
H20
-2-
-2.
-2^
Flowmeter readings
Initial
reading
(vs,),b
ft3 or
ft3/min
o.ow
0.0 &3
6.0530
Final
reading
/2<
                                                              -(Eq.2-l),Y =
                                                                                               -(Eq.2-2)
-(Eq. 2-3) ,Y =
               Vsl)/2]0[(tpl  +  tpf)/2'<


                 Figure 2.1A.  Flowmeter calibration data form  (English units).
                                                                                                •(Eq.2-4)
                                                                                                             T) O CO
                                                                                                             p p n>
                                                                                                             oq ft o
                                                                                                             (D (0 cr
                                                                                                                 H-
                                                                                                               «H O
                                                                                                             UJ C 3

                                                                                                               § 2!
                                                                                                                 O
                                                                                                               u> •
                                                                                                               o
                                                                                                               -  LO
                                                                                                              VD 
                                                                                                              OO-
                                                                                                              OOM

-------
Date   111 i  66    Calibrated by    /4?^     Meter  system no.   fl.0 -/6>    Primary meter no.
Barometric pressure, Pm =     "ft>/	 mm Hg Ambient  temperature   ,2-0.S"    °C
Type of primary meter: wet test 	X.   , dry gas 	
Type of flowmeter calibrated: rotameter   X   . dry gas  meter
                                                                                                   -j
                                                                   , or bubble meter
                                                                     , or mass  flowmeter
Primary meter readings
Initial
reading
(vpi),a
m3
0
0
0
Final
reading
(Vp,).'
Jft
2.0. 13
w.lfr
30-2t>
Initial
temp,°F
(W
°C
lo.S
1O ^
1d-(j>
Final
temp,°F

°C
ZO.'Z
2.0. 5"
ZO-b
Pres
drop
(Dp)'
mm
H20
-I5f)
~/30
-/3D
Flowoeter readings
Initial
reading
(V'"
mj or
m3 /min
rt.'S'
AO
/•S'
Final
reading
(V)b
m3 or
m3 /min
£>.£
l.o
I.Z
Initial
temp
(ttl)
°C
2.0.5"
Zo.(,
1,0.1*
Final
temp
(t.r>
°C
2^.5
ZD.(a
£0.6,
Press
drop
(Ds).c
mm
H20
0
0
0
Time
min
(e).d
min
4o&
ZO.V
zo.o
Calibration
factors
(YJ,6
0.114-
O.tU
OW*
(Y)
i*
—
OWL
a  Volume passing through the meter using the initial and final readings  and requires a minimum  of at
   least five revolutions of the meter.
b  Volume passing through the meter using the initial and final readings  or the indicated  flow rate
   using the initial and final flow rate setting.
c  Pressure drop through the meter used to calculate the meter pressure.
d  The time it takes to complete the calibration run.
e  With Y defined as the average ratio of volumes  for the primary  meter compared  to  the flowmeter
   calibrated, Yt = Y ^ 0.03Y for the calibration  and Yt = Y  + 0.05Y  for  the posttest checks;  thus.
   For calibration of the dry gas meter:
Y, =
                                            *.(Dp/13.6)]
                          tf)/2 * 2?3°K][Pn
(Eq.  2-5),  Y =
                                                                                              (Eq.  2-6)
                           pf
   For calibration of  the rotameter  and  mass  flowmeter:

                                "  273°K][PB  +  (Dp/13.6)]
      [u o en
                                                                                                            (B p 0)
                                                                                                            cq rt- r>
                                                                                                            0> O ct
                                                                                                                H-
                                                                                                              t-i O
                                                                                                            -P-C 3
                                                                                                                O
                                                                                                              OJ •
                                                                                                              O
                                                                                                              VD ON
                                                                                                              00-
                                                                                                              00 INJ
                                                 O

-------
Date    l(l
^\
Time
min
(O)/
min
ZO
-zo
ZO
Calculated
flow rate
CQ(std,]e
ft3 /min
O.O'bVb
O.G-B&C,
O.Ottio
Calibration
factor6
(K'J
^.02%
0- OVU,
O.bZQb
(K1)
1 __
	
O.OZf}(*
a  Volume passing through  the meter using the initial  and final readings and requires a minimum of at
   least five revolutions  of the  meter.
b  Volume passing through  the orifice using the initial and final readings or the indicated flow rate
   using the initial and final  flow rate setting (for  variable setting orifice only).
c  Pressure drop through the meter used to calculate the meter pressure.
d  The time it  takes to complete  the calibration run.
e  With K1 defined  as  the  average orifice calibration  factor based on the volumes of the primary test
   meter, K\ = K'  +_ 0.03K' for the calibration and K'A = K' ^ 0.05K'  for the posttest checks: thus,
   Flow  rate of  the primary meter at standard conditions:
   Vp
          17.71 (Vpf - Vpi)(Pm
                                    D/13.6)
      (std)
                                          (Eq. 2-9), Q(8td) =
                                                                  Vp
                                                                    (std)
            C(tpi + tpf)/2 + 460°F]

For determination of the K1 for the critical orifice:
                                                                     0
                                                                                           (Eq. 2-10)
                                              (Eq. 2-11),  & K'  =
                                                                       K'2 -i- K'3
                                                                                             (Eq. 2-12)
              Figure 2.2A.   Critical orifice calibration data form (English units).
                                                                                                            t? a w
                                                                                                            JO p (D
                                                                                                            W cr o
                                                                                                            (D CO rt
                                                                                                         Ul
                                                                                                               CD 2!
                                                                                                                 O
                                                                                                               CO •
                                                                                                               O
                                                                                                               «  LO
                                                                                                              VO ON
                                                                                                               O3 •
                                                                                                               CD N)

-------
Date   /////&&   Calibrated by
Barometric pressure, P_ =   ~/(fl
                                       	  Meter system no.  CO-(Z-   Primary meter no.
                                       nun Hg    Anbient temperature    ^J&.<£'    °C
Type of primary meter: wet test
                                    X-     , dry gas 	
Type of critical orifice: capillary glass     X «  needle or tubing
                    ,  or bubble meter
                                                                              , or adjustable
Primary meter readings
Initial
reading
(vpi>>a
L
0
0
o
Final
reading
(vpfKa
L
2.Z-/2-
ZZ--I3
2-Z-./2,
Initial
temp,°F

Pres
drop
<°P>
mm
H20
-/3o
-/3o
-730
Critical orifice readings
Initial
setting
b
L or
L/nin
flTL-ftJL
fined
fi-tefL
Final
setting
b
L or
L/min
/V//4
X/A
tflA
Press
drop
c
mm
Hg
4-ftD
57*
£30
Time
min
(e),d
min
2.0
•ZA
20
Calculated
flow rate
CQ(std,]e
L/min
/.0<7Z-
/.0?3
/.^>
 O
                                                     o
                                                          o

-------
                                                              Section No. 3.16.2
                                                              Date June 30, 1988
                                                              Page  7
     1.   The leak check  is  not conducted because  a leak may have  been corrected
         that was present during testing.
     2.  Three or more revolutions of the dry gas meter may be used.
     3.  Only two runs need be conducted at the average flow rate during the test.
     4.  Record  the  calibration check data on the appropriate posttest calibration
         check  data  form,  Figure  2.2A  (English units)  or  Figure 2.2B  (metric
         units).
     5.  If the posttest Y or K' factor agrees within 5% of the pretest factor, the
         flow meter  is acceptable.   If the factor does  not  agree due  to  a leak,
         correct  the leak  and recalibrate  the  flow  rate device.   The  reported
         results should then be  calculated using  both  the factor obtained with the
         leak and the factor obtained without  the leak.   If the  flowmeter does not
         pass the  calibration  check, the  metering  system must be recalibrated as
         described   above  for  the  initial  calibration.    Either  calculate  the
         emission results  for  the test report  using both factors or  consult with
         the Administrator.

2.1.4   Personnel Sampling Pump  -  Personnel  sampling pumps  are  used  to  collect
samples using  adsorption  tubes.   They should be calibrated  before  and  after the
field trip using a soap bubble meter as follows:
     1.  Set up the calibration apparatus as shown in Figure 2.3.
     2.  Check  the   pump  battery  with a  voltmeter  to  assure  adequate  voltage;
         charge,  if necessary.
     3.  Turn the pump • on and moisten  the  inner  surface of the soap bubble meter
         with soap  solution;  draw bubbles  upward  until  they  travel  the  entire
         length of the bubble meter without breaking.
     4.  Adjust the  pump  to  desired nominal flow rate.   Check the  manometer;  the
         pressure drop should not exceed 25mm Hg (13 in.)  water.
     5.  Start a soap bubble and measure the time  with a stopwatch that it takes to
         traverse at least 500 ml. Repeat at least twice more.  Average the results
         and calculate  the flow  rate by  dividing  the calibration  volume by  the
         average time.
     6.  Record the following data:
         a.  volume measured
         b.  elapsed time
         c.  pressure drop
         d.  air temperature
         e.  atmospheric pressure
         f.  serial number and model of the pump
         g.  date and name of operator
     7.  If the pump used for sample collection  uses  a rotameter,  the  calibrated
         flow rate must be adjusted for the ambient  pressure and  temperature during
         sampling:
                         V.
           =  Q
                                                                 Equation 2-17
         where
               V  =
               Q  =
               Q  =
               Pc  =
               P.  =
Corrected sample volume, liters.
Indicated flow rate, liters/min,
Sampling time, min,
Pressure during calibration, mm Hg,
Pressure during sampling, mm Hg,

-------
                               Tubing
          Soap
         Bubble
          Meter
         (1-Liter)
          Beaker
        Containing
          Soap
         Solution
                                                                                                Personnel
                                                                                                Sampling
                                                                                                  Pump
                                                            w
                                                            tO
                                                                                                                        •X) 0 CO
                                                                                                                           P CD
                                                                                                                           ft o
                                                                                                                           (B ft
                                                                                                                             H-
                                                                                                                           e-i O
                                                                                                                           C 3

                                                                                                                           CD Z
                                                                                                                             O
                                                                                                                           (jo •
                                                                                                                           O
O
                          Figure 2.3-   Personnel punp  calibration apparatus.
O
                                                                                                                          MD ON
                                                                                                                          00 •
                                                                                                                          co ru
O

-------
                                                               Section No.  3.16.2
                                                               Date  June  30,  1988
                                                               Page   9
               Tc  =
               T.  =
Temperature during calibration, °K, and
Temperature of sample gas, °K.
 2.2   Dilution System

 2.2.1  Dynamic  Dilution System - A dynamic dilution system may be required for  (1)
 preparation of  low concentration standards from high concentration standards or  (2)
 for  measuring  high  concentrations  of organic  emissions.   The  dynamic dilution
 system  must be  initially calibrated in the laboratory and then checked during each
 use.    To  prepare  the diluted calibration  samples,  calibrated  rotameters   are
 normally  used to  meter both the high concentration calibration gas and the diluent
 gas.   Other types  of  flowmeters  and commercially available  dilution systems  can
 also  be used provided  they meet  the performance criteria described below.
      The  following  steps should  be  used  to conduct the  laboratory calibration of
 the dynamic dilution system:
      1.   Assemble the  dilution system  (see Figure 2.4) as a unit using a calibrated
          rotameter or  mass  flow  meter for the calibration or stack gas in combina-
          tion with a  calibrated  rotameter, mass  flowmeter or dry gas meter for  the
          diluent gas.   It is  recommended  for dilutions up to 20 to 1 that a single
          dilution system be used.   For dilutions greater  than 20  to  1,  a double
          dilution system should be used.  It is also recommended that the system be
          assembled as  a unit  and not be disassembled between uses.  The rotameters
          should be  calibrated for the  range in  which they will  be  used following
          the calibration procedures described above.
      2.   Leak check  the  system  by  plugging  the  inlet  line  to  both rotameters,
          placing  the  dilution system discharge line  in a container  of water,  and
          turning  on  the sample  pump.  The  system is  leakless if no  bubbles  are
          released from  the discharge line.
      3.   The dilution system can be calibrated over the range that it will be used,
          however,  if   the  exact  dilution  to  be  used  is  known,  it is  better  to
          conduct a triple calibration at the desired dilution setting.   Attach the
          dilution system to the  diluent and  calibration gases.   Set the flowmeters
          to the desired rate  and fill the  bag with sufficient gas for GC analysis.
          Be careful not to  overfill the bag and cause  the bag to apply additional
         pressure on  the dilution system.   Record the  flow  rates  of both flowmet-
          ers ,   and  the  laboratory temperature  and  atmospheric  pressure  on  the
          dynamic dilution calibration form, Figure 2.5 or an equivalent form.
     4.  Analyze the diluted  calibration  gas and a calibration gas  that  is  in the
          same range as the  diluted gas.   The two gases must agree  within  10%  for
          the calibration point to be acceptable.   Repeat the calibration runs until
          acceptable results are obtained at all desired settings.

2.2.2  Static Dilution  System -  The  static dilution  system can be used for (1)  the
bag sampling  technique and  (2)  for  preparation  of low  concentration calibration
gases from  high concentration  cylinder gases.   The dilution  method for the  bag
sampling  technique is  used  to reduce the  concentration of organics  or water  vapor
in a gas  sample below  the condensation  point or for  safe  handling,  below the  lower
explosive limit.  Static dilution involves filling a bag with a diluent gas  using a
calibrated dry  gas meter or mass  flowmeter  and using  a syringe or  a rotameter  to
add the calibration gas or a sample  of stack gases to make a  lower concentration
calibration or sample  gas.
     The  following steps should  be used to  calibrate  a static dilution  system  in
the laboratory before  use:

-------
                                               Vont to Charcoal Adsorbers

                                           A        A                A
   Heated Lino
   from Proba
                   Quick
                  Connect
                                                                                                         Ftowmetors
                                                                                                         (On Outskia
                                                                                                           of Box)
 Chock Valvo
Quick Connects
 for Calibration
                                             Heated Box at 120* C or Sourco Tomporaturo
                                                                                                                          tj a w
                                                                                                                          B p (0
                                                                                                                          W ft O
                                                                                                                          O (6 ct
                                                                                                                               H-
                                                                                                                             «-i O
                                                                                                  To Hoslod GC Sampling Valvo    ^ *
                                                                                                                             -  u>
                             Figure 2.4.  Schenatic of heated box required for dilution of samples.
                                                                                                                             VO O\
                                                                                                                             co»
                                                                                                                             CO t\J
O
                            O
O

-------
                                                              Section No. 3.16.2
                                                              Date June 30, 1988
                                                              Page  11
Date ->YH/6b
Source flowmeter number P - J
Stage 1 flowmeter number G""(^«
Stage 2 flowmeter number * ////4
Barometric press /£»/ on (in.) Hg
Organic compound PcvcMorogilujLtHJu
Certified concentration 22yc> ppmv(X)
Calibrated by "7-ZX Gooctri'cl^

Date source meter calibrated // 2.0/88
Date stage 1 meter calibrated /
Date stage 2 meter calibrated
Heated box temperature iJuO
Leak check for total system C
Date of calibration curve 2-l\
/ 28/86
fJ/A
°C (°F
>£.
1/6&
„ .. , f f
STAGE 1
Emission gas flowmeter reading, ml/min
Diluent gas flowmeter reading, ml/min (
Dilution ratio
Injection time, 24h
Distance to peak, cm
Chart speed, cm/min
Retention time, min
Attenuation factor
Peak area or units
Peak area X attenuation factor
Measured concentration ,a ppmv
Calculated concentration,11 ppmv (Cs )
Percent difference,0 %
STAGE 2 (if applicable)
Emission gas flowmeter reading, ' ml/min
Diluent gas flowmeter reading, ml/min (
Dilution ratio
Injection time, 2kh
Distance to peak, cm
Chart speed, cm/min
Retention time, min
Attenuation factor
Peak area or units
Peak area X attenuation factor
Measured concentration,* ppmv
Calculated concentration,*1 ppmv
Percent difference,0 %
RUN 1 RUN 2
(qcl) Itt I^D
qdl) IODO IOOO
"?.(ff(*T- ^G>&>7-
'/03f fllT.
rf/A A//A
AJfA AJ/A
3. £3 3.$~4-
4- 4-
"50SO 2.160
/.X 'LOO II . (sf)0
3-l'l.e> ?'=l?:Z
'• 9 Aa '"} 0*0.
f—\)r> £-<3 -i
RUN 1 RUN2
(qr5) AifA- fJjA
g43) \ ' \

/
/ /
( '
\ /
) f
' \

/
/
\
RUN 3
/00D
TT (aft ?
l\4ft
AJ/A
tfIA
3-5"6»
4-
3>COO
I2..0C&
ZSf.J
28B
L 0. 3
RUN3
A//A
\
\
/
/
/
/
(




I
"• See Figure 5-1 for calculation.

       106 x (X x qc )
c Percent Difference =
= Calculated concentration for single stage

 Calculated Concentration - Measured Concentration

              Measured Concentration
                                                                         x 100#
  C  = 106 x X
                                                 = Calculated cone, for two stage
                      Figure 2.5. Dynamic dilution data form.

-------
                                                     Section No. 3-16.2
                                                     Date June 30, 1988
                                                     Page  12


Assemble  the static dilution system  (see Figure 4.3) and  leak check the
system  by plugging  inlet  to the  dilution system,  placing  the discharge
line in a container of water, and pulling a vacuum of about 1 in.  of Hg.
The system is leakless if no bubbles are released from the discharge line.
If the  system is not leakless, find the leak and correct it.
Calculate  as  the  amount  of diluent  gas needed  to  obtain  the  desired
dilution  or  calibration gas  concentration.   Meter the  desired amount of
gas into  the bag.   If the purpose of  the  static dilution  is to prepare a
lower  concentration of  calibration gas,  the calibration  gas  should be
added to the bag using a gas tight syringe.  Record the data on the static
dilution system data form,  Figure 2.6 or similar form.  If  the purpose of
the static dilution  system is  to collect  a diluted  stack  sample,  the
calculated amount of diluent gas  is added to  the bag  and the stack gas is
metered  into the  bag from  the  stack.    To  calibrate  this  system,  the
calculated amount of diluent gas should be metered into the bag and then a
calibration gas should be metered into the bag with the  flowmeter that is
to be used in the field.   Record the data on the static  dilution system
data form. Figure 2.6 or similar data form.
Analyze the  diluted calibration  gas  and analyze a different calibration
gas that  is  in the range of  the  diluted calibration gas.   The two gases
must agree within 10# of each other for the system to  be acceptable.
                                                                                     o
                                                                            o
2.3  Thermometer

     The  thermometers(s)  on the metering  systems and the  sample  probes and lines
should be initially compared with a mercury-in-glass thermometer that meets ASTM E-
1 No. 63C or 63F specifications:
     1.   Place the thermometer  to  be calibrated  and  the mercury-in-glass thermo-
         meter  in  a bath  of  boiling water.   Compare the  readings  after the bath
         stabilizes and then record  on the  calibration  data form. Figure  2.7 or
         equivalent.
     2.  Allow both thermometers to come to room  temperature.  Compare the readings
         after the thermometers stabilize.
     3.   The  thermometer is acceptable  if the values agree  within 3°C  (5.4°F) at
         both points.
     4.  Prior  to each  field  trip,  compare the temperature reading of the mercury-
         in-glass thermometer at room temperature with that of the thermometer that
         is part of the metering system.  If  the values are not within 6°C (10.8°F)
         of each other, replace or recalibrate the meter thermometer.

2.4  Barometer

     The field  barometer  should be adjusted  initially and  before  each test series
to agree within 2.54 mm (-0.1 in.) Hg with a mercury-in-glass barometer or with the
pressure value reported from a nearby National Weather Service Station and correct-
ed for  elevation.   The  tester  should be  aware  that the National  Weather Service
readings  are  normally  corrected  to  sea  level;  uncorrected  readings  should  be  x—x
obtained.  The  correction  for the elevation  difference  between the weather station  f   j
and the  sampling  point should be applied  at a rate  of  -2.5 mm Hg/30 m (-0.1  in.  V_y
Hg/100 ft) elevation increase,  or vice versa for elevation decrease.

-------
                                                              Section No. 3.16.2
                                                              Date June 30, 1988
                                                              Page  13
Date
Source flo^metJer number 	
Dry gas meter number   QM~ l~7
Ambient temperature
Barometric press
Organic compound
Certified concen, (X)  2.2-/Q  /ppmv
                        mm  (in.) Hg
Calibrated by 	
Date source meter calibrated _
Date dry gas meter calibrated
Dry gas meter calib factor (Y)
Leak check for total system 	
Vacuum during leak check
Date of calibration curve
                                                                         ///#/ 88
                                                                            ~
                                                                     /& /*.
Initial dry gas meter reading, L  (ft3)
Final dry gas meter reading, L (ft3)
Volume of diluent gas metered, L  (ft3)
Gas metered X calibration factor  (Y),{V2}
Flowmeter sampling rate, L/min (cfm)
Sampling time, min
Sampling rate X sample time, L (ft3),{V1)
Dilution ratio
Injection time, 24h
Distance to peak, cm
Chart speed, cm/min
Retention time, min
Attenuation factor
Peak area or units
Peak area X attenuation factor
Measured concentration," ppmv
Calculated concentration,1* ppmv,   {Cs}
Percent difference,0  %
                                                RUN 1
                                                             RUN 2
                                  RUN
                               IB3.
                                              /3 Z-
                                                            J2-/.6>/3
                                               O.
                                                 2.0
                                 2-0
                                               3.04-
                                                            &.//0
                                                             2-6.6
                                                ID
                                               30 5P
*  See Figure 5-1 for calculation.

b  Calculated concentration (Cs) =
                                         X (Vt)
                                              Va)
                                                                      ppmv
                             Measured concent - Calculated concent
0  Percent difference,
                                                                    X 100
                                     Measured concentration

   The percent difference must be less than 10 % absolute.
                      Figure 2.6.   Static dilution data form.
                                                31

-------
Date
to/to
fio/M






Reference
thermometer
type
*w
*%£






Calibr
thermc
type
tS&
~fat.fiw-
CeufilJL,
1





ated
meter
use
sh*
htefar






no.
WHZ
?-z






Ambien
refer"
<#F
MT-






t temper
calibr"
•fi-P
JO'F






Measurec
ature
differ0
'w
+-!'!=






values
Boi
refer*
wr
Z/2"/r






ling wat
calibrb
3&F
*ll'f






er
differc
i-i-fi
-\'F






Calibrator's
initials
ATA1
A77V






                                                                                                            TJ o en
                                                                                                            £8 P (D
                                                                                                            Oq c* O
                                                                                                            0) (D ct
  Temperature reading of the reference thermometer in °C or °F.
  Temperature reading of the thermometer being calibrated in °C or °F.
  Difference between the reference thermometer and the calibrated thermometer.  This difference must
  be less than 3°C (5.4°F)  for than initial calibration and 6°C (lO.lpF) for the calibration check.
                              Figure 2.7-  Thermometer calibration fora.
O
                                                            o
                                                          CO «
                                                          o
                                                          -  UJ
                                                          U3 ON
                                                          OO •
                                                          OOI\i
o
o

-------
                                                              Section No. 3.16.2
                                                              Date June 30, 1988
                                                              Page  15
              Table 2.1.  ACTIVITY MATRIX FOR CALIBRATION OF EQUIPMENT
Apparatus
Wet  test meter
Dry gas meter,
mass flow meter,
and rotameters
Critical orifice
Dilution system
Thermometers
Barometer
 Acceptance  limits
Capacity of about 2
L/min and accuracy
within  12
Y£ = Y + 0.03Y at a
point greater than
the flow rate range
to be used
K'i = K ± 0.03K'
Measured value for
diluted and undi-
luted calibration
gas must agree
within 10*
Within 3°C (5.
of true value
Within 2.5 mm
{0.1 in.) Hg of
mercury-in-glass
barometer or weather
station value
Frequency and method
   of measurement
 Calibrate initially,
 then yearly by
 liquid displacement
                       Calibrate vs. wet,
                       dry, or bubble meter
                       upon receipt and
                       after each test
                       Calibrate vs. wet,
                       dry, or bubble meter
                       upon receipt and
                       after each test
 Calibrate upon
 receipt and prior to
 each field test using
 calibration gases
 Calibrate initially
 as a separate com-
 ponent with mercury-
 in-glass thermometer;
 check before each
 test against mercury-
 in-glass thermometer
 Calibrate  initially
 using mercury-in-
 glass barometer;
 check before  and
 after each test
                                              Action if
                                              requirements
                                              are not met
                                              Adjust until
                                              specs are met, or
                                              return to vendor
                        Repair and
                        then recalibrate,
                        or replace
                        Repair and
                        then recalibrate,
                        or replace
                                              Correct problem
                                              and rerun cali-
                                              bration
                                              Adjust or replace
                                              Adjust to
                                              agree with
                                              certified
                                              barometer

-------
o
o
o

-------
                                                                 Section No. 3.16.3
                                                                 Date June 30, 1988
                                                                 Page 1
 3.0  PRESAMPLING  OPERATIONS
       This section  addresses  two  major areas of presampling operations for Method
 18:  (1)  preparation  for,  performance  of,  and interpretation  of results  for  the
 preliminary survey and (2) preparation  for  the  final sampling.  This  section  de-
 scribes  the preliminary survey as  it applies to Method 18;  for additional general
 information on preliminary surveys,  see Section  3«0  of  this  Handbook.   The quality
 assurance  activities  for  the preliminary  survey activities  and the  presampling
 activities for final testing are summarized in Tables 3«1 and 3«2, respectively, at
 the end  of this section.

 3.1  Preliminary Survey Measurements

       The preliminary survey  measurements are needed to  properly design the final
 emission test sampling and analysis protocol.  The primary objective of the prelim-
 inary survey is to collect a preliminary survey sample for determining which sampl-
 ing procedure  is  most appropriate and  for developing the optimum analytical pro-
 cedures.   Using  the preliminary survey sample, estimates of  the source concentra-
 tion are made  and the major organic components  in the gas stream are  identified.
 Also, any  compounds that may  interfere  with the quantitation of the target anal-
 yte(s) are identified  and  the  appropriate  changes  in the  analytical  procedures  are
 made.  Other measurements made during the  preliminary survey  include sampling site
 dimensions and gas  stream properties.    The preliminary survey is  also used  to
 obtain a description of the process being sampled,  to determine sampling logistics,
 and, when  possible,  to collect bulk process samples and  use  emission  screening
 techniques.  Use the data form shown in Figure 3-1 to record the preliminary survey
 information.

 3.2  Preliminary Survey Preparation

     This  section addresses  the equipment  and  preparatory  activities needed  to
 conduct  the preliminary survey.   Figure 3.2 can serve  as an  equipment checklist,
 packing  list,  and/or equipment status form for the preliminary survey.

 3.2.1  Measurement  of Flue Gas Properties - The apparatus that  may  be  required to
 supplement information obtained  from plant personnel  during  the preliminary survey
 concerning the moisture  level,  temperature,  and static pressure  of  the  source
 should be prepared for the preliminary survey as  follows:

     Barometer -  The  field barometer should be compared with  a  mercury-in-glass
 barometer or with  a National  Weather Service Station (see Subsection 2.4)  reading
 prior to each field test.

     Net Bulb/Dry Bulb Thermometers - It is recommended  that for sources with stack
 temperatures  at or below 59° C, wet bulb/dry  bulb thermometers  be used to  determine
 stack gas moisture content. The  thermometers  should be compared  with a  mercury-in-
 glass thermometer at  room  temperature prior  to each field trip.  The wet  bulb/dry
 bulb measurement may also be used,  with  the prior approval of  the Administrator,  to
 determine stack gas moisture for sources where the  stack temperature  exceeds  59° C.

     Method 4  Equipment - For  sources with stack temperatures  above  59°C, Method 4
equipment is recommended to determine stack gas moisture content.  Prepare  the
                                           . .  /"/ ••? ('' )
                                                    '

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                                                         Section No.  3.16.3
                                                         Date June 30,  1988
                                                         Page 2
I.  Name of company 	 Date_
    Address
    Contacts                                 Phone
    Process to be sampled
    Duct or vent to be sampled
II. Process description
    Raw material
    Products
    Operating cycle
         Check:  Batch	Continuous	Cyclic_
         Timing of batch or cycle	
         Best time to test	
III.  Sampling site
     A.  Description
         Site description	
                                                                                     o
         Duct shape and size
         Material
         Wall thickness	inches
         Upstream distance	inches	_diameter
         Downstream distance	inches	diameter
         Size of port	
         Size of access area
         Hazards	Ambient temp_
     B.   Properties of gas stream
         Temperature	°C	°F,   Data source_
         Velocity_	,  Data source_
         Static pressure	inches H20,  Data source_
         Moisture content              %,  Data source
         Particulate content	,  Data source	
         Gaseous components
            N2	%  Hydrocarbons (ppm)    Toxics/Acids  (ppm)
            02	%  	     H2S
                    CO	%  	     HC1 __
                    C02	%  	     HF  _
                    S02	%  	     Other

                    Figure 3-1-  Preliminary survey data sheet.

(Continued)
                                                                            O

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                                                                 Section No. 3.16.3
                                                                 Date June 30, 1988
                                                                 Page 3
 Figure  3.1  (Continued)

                 Hydrocarbon components
                                                            ppm
                                                            ppm
                                                            ppm
                                                            ppm
                                                            ppm
                                                            ppm
             C.  Sampling considerations
                 Location to set up GC
                 Special hazards to be considered_
                 Power available at duct_
                 Power available for GC
                 Plant safety requirements
                 Vehicle traffic rules
                 Plant entry requirements
                 Security agreements_
                 Potential problems
                 Safety equipment (glasses, hard hats, shoes, etc.)
             D.  Site diagrams.  (Attach additional sheets if required).

        IV. On-site collection of preliminary survey samples
             A.  Evacuated flasks
                 Flasks have been cleaned,  heated in furnace and purged
                 with nitrogen?	
             B.
(Continued)
                 Flask evacuated to the capacity of pump?	
                 Filter end of probe placed at center of stack,  probe
                 purged and sampled collected into flask until flask is at
                 stack pressure?	
                 Stopcocks closed and taped?	
                 Duct temperature and pressure recorded?	
Purged flasks
Flasks cleaned and purged with nitrogen?	
Filter end of probe placed into stack, sample purged for
2 to 5 min and then stopcocks closed?	
Stopcocks taped to prevent leakage?	
                 Duct  temperature and pressure recorded?	
                 Stability and adsorption  checks  conducted?^

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                                                                 Section No. 3.16.3
                                                                 Date June '30,  1988
                                                                 Page 4
o
Figure 3^1  (Continued)
             C.  Flexible bags
                 Bags have been blanked checked and leak checked?_
                 Sampling system leak checked?	
                 Filter end of probe placed into center of stack and sample
                 obtained at a proportional rate for appropriate amount of
                 time?	
                 f>uct temperature, barometric pressure, ambient temperature,
                 flow rate, static pressure, and initial and final sampling
                 time recorded?	
                 Analysis performed within 2 hr?	
                 Stability and adsorption checks conducted?	
             D.  Adsorption tubes
                 Proper adsorption tube(s) selected based on the likely
                 analytes?	
                 Probe or adsorption tube placed into center of stack and
                 sample obtained at a constant rate with a calibrated
                 system for appropriate time based on the expected concen-
                 trations of analytes?	
                 Total sample time and sample flow rate (or the number of
                 pump strokes),  the barometric pressure, and ambient
                 temperature recorded?	
O
                 Water vapor was less than 2% or measures were taken to
                 protect or increase the adsorption capacity of the
                 adsorption tube(s)?	
             E.  Quality assurance performance audit samples
                 Quality assurance audit samples collected in the same
                 manner as the emission samples?	
             F.  Bulk samples and screening techniques
                 Bulk emission sample(s) collected?	
                 Bulk liquid sample(s)  collected?
                 Detector tubes or other screening techniques used?
                                                                                       O

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                                                                 Section No. 3.16.3
                                                                 Date June 30, 1988
                                                                 Page 5
Apparatus check
Moisture Determination
W Bulb/D Bulb
Checked
Barometer
Calibrated*
Method 4
Probe, heated &
leak checked
Imptngers
Meter system
calibrated*
Velocity Determination
Pitot Tube
Number
Length
Pressure Gauge
Manometer
Other
Stack Thermometer
Calibrated 	
Evacuated Flask
Evacuated Flasks
Number
Cleaned
Oven heated
N2 purged
Probes
Number
Cleaned
Glass wool
Suction bulb
Pump
Purged Flask
Flask
Number
Cleaned
Oven heated
N2 purged
Acceptable
Yes




No




Quantity
Required




Ready
Yes




No




Loaded and Packed
Yes




No




*Most significant items/parameters to be checked.

                   Figure 3-2.  Preliminary survey preparations.
(Continued)

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                                                                 Section No. 3.16.3
                                                                 Date June 30, 1988
                                                                 Page 6
o
Figure  3.2   (Continued)
Apparatus check
Purged Flask (continued)
Probe
Number
deemed
Glass wool
Vacuum Source
Pump
Squeeze bulb

Bag Sampling
Probe Liner
S steel
Glass
Teflon tube
Length
Meter System
Flowmeter*
Pump
Evacuated can
Charcoal tube
Sample line
Tedlar Bags
Number
Blank checked
Leak checked*
Heated Box
Number
Heat checked
Adsorption Tube
Probe
Heated
Checked
Nonheated
Glass
S steel
Filter
Sample Line
Type
Length
Checked*
Acceptable
Yes



No



Quantity
Required



Ready
Yes



No



Loaded and Packed
Yes



No



                                                                                      O
*Most significant items/parameters to be checked.

(Continued)
O

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                                                                 Section No. 3.16.3
                                                                 Date June 30, 1988
                                                                 Page 7
Figure 3.2   (Continued)
Apparatus check
Adsorption Tube (continued)
Pump and Meters
Pump
Orifice
Calibrated*
Rotameter
Calibrated*
Timer
Adsorption Tubes
Tw>e

Bulk Samples
20-ml Jars .
Cleaned
Acceptable
Yes


No


Quantity
Required


Ready
Yes


No


Loaded and Packed
Yes


No


*Most significant items/parameters to be checked.

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                                                                 Section No. 3.16.3
                                                                 Date June 30, 1988
                                                                 Page 8                 /""X

equipment for sampling  following the procedures described in Section 3'3-3 of this     ^—
Handbook.  Method 4  equipment may also be used to determine the stack gas moisture
for sources where the stack temperature is at or below 59°C.

     S-Type Pttot Tube  and Differential Pressure Gauge  -  Prepare  the S-type pitot
tube and the differential  pressure gauge  for sampling following the procedures de-
scribed in Section 3'1«3 of this Handbook.

3.2.2  Glass Flask  Sampling - The apparatus and  reagents  required for the collec-
tion of  preliminary  survey samples  using glass sampling  flasks  are  prepared  as
described below.  Alternative equipment found suitable  may  be  used  subject to the
approval of the Administrator.

     Probe - If a heated probe is to be used for sampling, then the probe's heating
system should be checked to see that it is operating properly.  The probe should be
cleaned internally by brushing first with tap water,  then with deionized distilled
water, and finally with acetone.   Allow the probe to air dry.  The probe should be
sealed at the  inlet end and  checked  for  leaks by applying  a vacuum  of 380 mm (15
in.) Hg.   See Subsection  1.0 for leak check  procedure.  The  probe  is considered
leak free under these  conditions  if no loss  of  vacuum is  seen after one minute.
Any  leaks  detected  should be corrected  or the probe  should be  rejected.  If the
probe has an external sheath,  the integrity of the seal between the sheath and the
probe liner should be checked to ensure ambient air does not dilute the gas sample.
     Teflon Tubing  -  Prepare sections of tubing  for  connections between the probe
and each  flask  (or  bag or tube) that  constitutes  a preliminary survey sample col-
lection  device.   Clean the  tubing using  the procedure  described above  for the
probe.

     Quick Connects - The  quick connects  should be new or cleaned according to the
manufacturer's  recommendations.   Leak check  the quick  connects as  described in
Subsection 1.0.

     Glass  Sampling Flasks  -  Prepare the  glass sampling  flasks  for collecting
preliminary survey samples as  follows:  Remove the stopcocks from both ends of the
flasks, and wipe the parts to remove any grease.  Clean the stopcocks, barrels, and
receivers with chloroform.   Clean  all  glass parts with a soap solution, then rinse
with tap  water  followed by deionized distilled water.  Place  the flasks in a cool
glass annealing furnace  and  heat the  furnace to 550°C.  Maintain the flasks in the
oven at  this  temperature  for  one  hour.    After  one hour,  shut off and  open the
furnace  to  allow the  flasks to cool.   Return the  Teflon stopcocks  to  the glass
flasks (if glass stopcocks are  used,  apply  a light coating of vacuum grease to the
stopcocks before returning to  the  flasks.)   With both stopcocks  open,  purge each
assembled flask with high purity nitrogen for 2 to 5 minutes.  Close off the outlet
stopcock  followed  by  the  inlet stopcock  to maintain  a  slight  positive  nitrogen
pressure in the flask.  Secure  the stopcocks with tape to prevent them from opening
accidentally.

     High-Vacuum Pump -  A  high-vacuum  pump  will be required  for preliminary survey
sample collection using  the  evacuated  flask procedure.  Check  the operation of the
pump prior to going to  the field as follows:  Check  for minimum pump  vacuum of 75
mm (3 in.) Hg absolute by attaching a Hg-filled U-tube manometer to the pump inlet
o
o

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                                                                 Section No. 3.16.3
                                                                 Date June 30, 1988
                                                                 Page 9

and  turning on the pump.  If the minimum  vacuum  cannot  be reached, then repair or
replace the pump.

     Rubber  Suction Bulb - A rubber suction bulb will be required for preliminary
survey sample  collection using the purged  flask procedure.  The rubber suction bulb
should  be checked  for  proper operation prior to going to the field  as follows:
Attach  the  bulb to a water manometer, or  equivalent, and squeeze  the bulb until a
vacuum  of at least 250 mm (10 in.) H20 is reached.   Repair or replace the squeeze
bulb if sufficient  vacuum cannot be developed.

3.2.3  Flexible. Bag Procedure - A flexible bag of Tedlar or aluminized Mylar can be
used to collect preliminary  survey  samples.   If it is anticipated that Tedlar bags
will be selected  as  the final  sampling  method,  then it is  recommended that the
preliminary  survey sample be  collected using  a Tedlar bag.   In  addition  to the
apparatus described in Subsection 3.2.2 for the glass flasks (with the exception of
the  flasks  and the high-vacuum  pump)  the  apparatus listed below  will  be required
and should be  prepared as follows:

     Tedlar  or Aluminized Mylar Bags  -  Prepare  new  bags for  preliminary survey
sampling by leak checking the bags before  going to the field.  The bags should also
be  checked  for  contamination by  filling with  hydrocarbon-free  air or nitrogen
during  the  leak check.   The bags are checked  as  follows:   Connect a water manome-
ter, or equivalent, using a tee connector,  between the check valve quick connect on
the bag and a pressure source (or hydrocarbon-free air  or nitrogen for conducting
the contamination check).  Pressurize the  bag to 5 to 10 cm (2 to 4 in.) H20.  Loss
of pressure over a  30-second period indicates a leak.   Alternatively, leave the bag
pressurized  overnight:  a deflated bag  the following  day is indicative  of a leak.
Reject or repair  any  bags with leaks.  After  the hydrocarbon-free air or nitrogen
has remained  in the bag for 24  hours,  analyze the bag contents using a GC with a
flame ionization  detector on the most  sensitive  setting.   The bag  should  be re-
jected  if  any organic  compounds   are  detected.   If  any  organic  compounds  are
detected,  the  bags may  be  used if they are not  the  compounds to be  sampled and
analyzed.

     Rigid Leak-Proof Containers -  Rigid  containers can be used with the bags for
collecting  preliminary  survey samples. The rigid containers  used to contain the
Tedlar  bags  during sampling  should be  checked• for  leaks prior  to  going  to the
field.   The container should  be leak  checked with the  bag  in place as follows:
Using a tee connector, connect a water  manometer  or equivalent,  between a pressure
source and  the container outlet.  Pressurize  the container to 5 to  10  cm (2 to 4
in.) Hg.  Any loss of pressure after 30 seconds indicates a leak.  Reject or repair
the rigid container if a leak is indicated.

     Direct Pump  Sampling System - A  direct pump  sampling system can be  used  in
place of  the rigid containers for  collecting preliminary survey  samples.  If this
method is selected, then  the  system should be assembled and leak  checked prior  to
going to  the  field  as  follows:   Assemble  the system  (see  Figure 4.5).   Bypass the
Tedlar bag and its protective container by  attaching the  vacuum line directly after
the rotameter  using the quick connects  on the sample and vacuum lines.  Plug the
probe inlet and  turn  on the  vacuum  pump.    If  the  system is  leak  free,  the
rotameter should eventually indicate no flow.  Alternatively,  the  sample line that
is attached to the  sample bag can be placed in water.  If bubbling stops,  then the
system is  leak free.

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                                                                 Section No. 3-16.3
                                                                 Date June 30. 1988
                                                                 Page 10

     Needle Valve  and Eotameter - Prior to  each  field trip or at  any  sign of er-
ratic behavior,  the flow control valve and  the rotameter  should  be cleaned accor-
ding to the maintenance procedure recommended by the manufacturer.

3.2.4   Adsorption  Tube Sampling - The adsorption  tube sampling procedure can also
be used to collect the preliminary  survey  sample.  If it  is  anticipated that ad-
sorption  tubes  will be selected as  the final  sampling method, then it  is recom-
mended  that the preliminary survey samples be collected using tubes containing each
potential  type  of  adsorbent.  In  addition  to  the apparatus described  in Section
3.2.1 for the glass  flasks (with the  exception  of  the  flasks and  a  high-vacuum
pump) the apparatus listed below will be  required and should  be  prepared as fol-
lows:

     Adsorption Tubes - Check to see that the proper type of tube has been obtained
for collecting the  target organic compounds.  Refer to Table B in the Methods High-
lights  Section to  determine  the proper adsorption material.  Check to see that the
supply  of adsorption tubes is  sufficient  to conduct  the  emission test,  including
field blanks and desorption efficiency determinations.

     Personnel Sampling Pump -  A personnel sampling  pump is used to  collect the
adsorption  tube  samples.   The  pump  should be  calibrated  following the procedures
described in Subsection 2.1.4.

     Extraction Solvents  -  An extraction solvent  will be  required to  prepare the
preliminary survey  adsorption tube sample(s) for analysis.  Refer to Table B in the
Methods Highlights  Section to determine the proper extraction solvent.

3.3  Preliminary Survey Sample Collection

     The  preliminary  survey sample  collection  includes flue gas  or  duct moisture
and velocity  determinations  in addition to  collection of actual  flue  gas or duct
samples.

3.3-1   Preliminary Survey Moisture Determination - If  the  moisture content of the
flue gas  in the  duct to be tested cannot be obtained  from the plant  personnel,  it
is determined using  either  wet bulb/dry  bulb thermometers  or Method 4 sampling
apparatus,  depending  on  the  flue gas temperature.    If  the flue  gas  temperature
cannot  be  obtained from plant  personnel,  then determine the  flue gas  temperature
using a calibrated thermocouple, thermometer, or  equivalent  temperature  measuring
device.

     Net  Bulb/Dry  Bulb Procedure  -  For  flue gas  streams at  or  below  59° C,  the
moisture  content  of  the  flue  gas  should be  determined  using wet bulb/dry  bulb
thermometers  and  the partial  pressure  equation shown  below.    Obtain the  wet
bulb/dry bulb temperatures as follows:
     1.  Moisten the wet bulb thermometer wick with deionized distilled water.
     2.  Insert the  thermometers  into the  flue gas stream and monitor the wet bulb
        temperature.
     3.  When the wet bulb temperature has stabilized,  record  both  the wet bulb and
        dry bulb thermometer temperatures.
     4.  Calculate the flue gas moisture content using the equations below.
o
o

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(t
                                   -(31AA/(Tw*390.86)
                                                                 Section No. 3.16.3
                                                                 Date June 30,  1988
                                                                 Page 11

                                                                       Equation 3-1
                   w2  =
                   %U20  = w2  -  (0.00036? x  (Td-Tw) x  (l+(Tw-32)/1571)) x 100

               where
                                                                       Equation 3-2
                  w  =
                  P. =
Calculated constant, saturation % H20 at Tw
Wet bulb temperature, °F,
Dry bulb temperature, °F,
Barometric pressure, in. Hg, and
Static pressure of duct, in.
                                          H20.
     Method 4 Moisture Procedure  -  Follow the procedure for Method
Section 3-3 of this Handbook.
                                                                                 described in
               Method 2  Velocity Procedure - Follow the procedure for  Method  2 described in
          Section  3-1  of this  Handbook to determine  the  flue gas  or  duct velocity  at the
          sampling  point.    If the  velocity  varies by  more than  10%  during  the projected
          sample run  time,  then proportional sampling will be required as  described in Sub-
          section 4.0.   Because of the small  size  of  some ducts, Methods  2A,  2C,  or 2D may
          have to  be  used.   Follow  the criteria and procedures  described  in  the applicable
          method.

          3.3.2   Collection of Samples with  Glass Sampling Flasks -  Using  the precleaned
          glass sampling flasks, preliminary survey samples are collected using the evacuated
          flask procedure or the purged flask procedure.

               Evacuated  Flask  Procedure  -  Collect preliminary survey  samples using the
          evacuated flask procedure as follows:
               1.   Using a high-vacuum pump  which is connected to one stopcock  while the
                    other stopcock remains  closed, evacuate  each   precleaned  flask  to the
                    capacity of the  pump.   A mercury manometer can  be  connected between the
                    pump and  the flask using  a tee connector  to indicate when  the maximum
                    vacuum is achieved.  At this point, record  the vacuum,  and close off the
                    stopcock leading to the pump.
               2.   Remove the  tubing  leading  to the pump and attach a glass  tee (6-mm out-
                    side diameter, or  equivalent)  to the  flask  inlet with a short  piece of
                    Teflon tubing.
               3.   Connect the end  of the  sampling probe  to  the  glass  tee  using  a short
                    length  of  Teflon  tubing.   The  tubing must be  of  sufficient  length to
                    reach the sampling point at the  centroid of or no closer than 1 meter to
                    the duct wall.
               4.   Connect the rubber suction bulb  to the third  leg of the tee with a piece
                    of Teflon tubing or suitable flexible tubing.
               5.   Place a plug of glass wool in the probe  inlet, enlarged to approximately
                    12-mm outside diameter, to serve as  a filter to remove particulate mat-
                    ter.
               6.   Place the  inlet  (filtered) end  of  the probe at the sampling point  and
                    purge the probe  and sample line by repeatedly squeezing the  rubber suc-
                    tion bulb until at least 7 air changes of the probe and sample line have
                    occurred.

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                                                                 Section No. 3.16.3
                                                                 Date June 30, 1988
                                                         :        Page 12

     7.   After  the  probe  and the sample  line are  completely purged,  leave  the
          squeeze bulb in place, and open the inlet stopcock of the sampling flask
     8.   Leave  the  inlet  stopcock open until the pressure  in the sampling flask.
          reaches the duct pressure.  This should take about 15 seconds.  Close the
          inlet stopcock.
     9.   Remove  the probe  from  the duct  and disconnect the glass tee  from  the
          flask.
     10.  Taps the stopcocks closed and  label  the  flask with the plant name, date,
          and sampling location, time, and sampling personnel.
     11.  Immediately  after sampling, determine  the flue gas temperature  with  a
          calibrated thermocouple, thermometer, or equivalent  temperature measuring
          device, and  determine the static pressure  of the duct  and the velocity
          over a period of  time equal  to the predicted sample  run time following
          the procedures described in Section 3-1 *n this Handbook.

      Purged Flask Procedure - Collect preliminary survey  samples using the purged
flask procedure as follows:                                       ,
     1.   Connect the  small end  of  the sampling probe,  of  sufficient  length to
          reach  the  centroid of the duct to be sampled, to the inlet stopcock of a
          precleaned glass sampling flask a sufficient length of Teflon tubing.
     2.   Connect the  rubber  suction bulb  to the other stopcock with  a piece of
          Teflon tubing or suitable flexible tubing.
     3.   Place  a plug of  glass wool  in  the probe  inlet,  enlarged to approximately
          12-mm OD,   to serve as a filter to remove particulate matter.
     4.   Place  the  inlet  (filtered) end of  the  probe at  the centroid of  or no
          closer than 1 meter  to the duct wall.
     5-   Purge  the  probe, sample line,  and  sample flask by  repeatedly squeezing
          the rubber suction bulb until approximately 7 air changes of the system
          have occurred.
     6.   After  the  probe,  sample  line,  and flask  are completely purged, close off
          the stopcock near  the suction  bulb,  and  then  close off the stopcock con-
          nected to  the probe.
     7.   Remove  the probe  from  the  duct,  and disconnect both the  probe  and  the
          suction bulb from the flask.
     8.   Tape the stopcocks closed and  label  the  flask with the plant name, date,
          and sampling location, time, and sampling personnel.
     9.   Immediately  after sampling, determine  the flue gas temperature  with  a
          calibrated thermocouple, thermometer, or equivalent temperature measuring
          device, and  determine the static pressure  of the  duct  and the velocity
          over a  period  of time equal to the predicted sample  run time following
          the procedures described in Section 3*1 in this Handbook.

3.3-3   Flexible  Bag Procedure -  The flexible  bags used  to  collect  preliminary
survey samples must  be leak checked  and demonstrated to be  free  of contamination
following the  procedure described in Subsection  3-2.2.   The  preliminary survey
sample collection using flexible bags can be conducted at a constant rate following
the  procedure  described in Subsection  4.3 for the  evacuated  container sampling
procedure, the direct  pump sampling procedure, or, in  explosive  areas,  the explo-
sion  risk area  sampling  procedure.   The  flue  gas or  duct  velocity  and  other
process parameters should  be  determined  for  designing the  final  sampling proced-
ures.
o
 o
 o

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                                                                 Section No. 3.16.3
                                                                 Date June 30, 1988
                                                                 Page 13

3-3-4   Adsorption Tube Procedure  -  The adsorption tubes used  to  collect the pre-
liminary survey sample(s)  should  contain the adsorbent specified in Table B of the
Method  Highlights Section for the  target analyte(s).   The sampling time or total
sample  volume  for the adsorption tube  should be  calculated based  on expected con-
centration (s)  of  the volatile organic(s)  present and  the recommended  capacity of
the  adsorption media.   Refer to the  appropriate reference given  in Table  B to
determine the  recommended sample  volume taking  into  consideration  the  amount of
adsorbent to be used.  For compounds not referenced in Table B, use  a reference for
a compound  with  similar chemical characteristics.  If the  target  analytes require
different adsorption  media,  then  it is recommended that preliminary survey samples
be  collected using each  type of  adsorbent.   In the  case  where  the  compound is
unlike  any  other  documented  compounds, use  two adsorption tubes connected in ser-
ies.    Once a recommended  volume  is  established,  it  is   recommended   that  two
additional  samples  be collected  with  sample  volumes  one  half  and  twice  the
recommended volume.      The procedure  for collecting preliminary survey adsorption
tube samples is as follows:
     1.   Open the adsorption tube,  and connect  the  primary  tube  section (large
          section  of  adsorbent)  to  the sampling  probe  using a minimum  length of
          Teflon tubing or other nonreactive tubing.
     2.   Connect  the outlet  (backup  section) of the  tube  to the next  tube in
          series,  if additional adsorption capacity is required.
     3.   Connect  the outlet  of  the last tube to  the  inlet of the calibrated per-
          sonnel sampling pump using a  sufficient length of tubing.
     4.   Insert  the  probe into  the stack or duct and  turn on the pump.   Maintain
          the  adsorption  tubes in  a  vertical position during  sampling to prevent
          channeling.   Sample the gas  stream  for the time required to obtain the
          optimal volume determined from the referenced method.
     5.   Immediately after  sampling is  completed,  disconnect the  tubes from the
          tubing  and  seal  the tube ends with teflon tape and plastic caps.  Label
          the  tubes  and store each tube in a screw  cap  culture tube or similar
          container to protect them during shipment.
     6.   Record  the  total  sampling time,  the sample  flow  rate,  the barometric
          pressure, and the ambient temperature.

3-4  Preliminary Survey Sample Analysis and Interpretation

     With the  exception of the analysis of  the glass  sampling flasks, the analysis
of preliminary survey samples  should follow the procedures  described in Subsection
5-0.  The analysis of the glass sampling flasks are described below  (see Subsection
3-4.2).   The  analysis of  preliminary survey  samples is  used  to optimize  the
analytical procedures and  select  the most appropriate sampling technique for final
sampling.   Using  Table C  the Method  Highlights Section,  choose  appropriate GC
detector(s).   Based  on the  sampling technique(s)  used to collect the preliminary
sample, choose a  GC  column  from the  selections  listed in Table  D  of the Method
Highlights  Section;  the technical  service  department  of  column  manufacturers or
plant  laboratory  personnel  may  also  be consulted for additional  suggestions on
column  type(s).    For glass   flask  samples  and Tedlar or Mylar bag samples,  use
calibration  gas cylinders  or calibration standards prepared  in Tedlar bags.   For
adsorption  tube   samples,  prepare  the calibration   standards  directly  in  the
desorption liquid(s)  or on adsorption tube material(s)  used  to collect the samples.

3.4.1  Calibration Standards for Preliminary Survey Samples - Prepare a minimum of
three calibration  standards  for  each compound  of  interest.   The  standards should

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                                                                 Section No. 3.16.3
                                                                 Date June 30, 1988
                                                                 Page 14

cover a  linear range for the particular GO detector,  with the lowest standard and
the highest standard bracketing and a midrange standard approximating the expected
sample concentration.   To estimate the sample concentration,  prepare a preliminary
survey sample  and perform a single analysis  of  the  sample following the procedure
in  the  appropriate  subsections  below. During this  sample analysis,  determine if
adequate resolution  has been achieved for each peak with  a peak area greater than
5#  of the  total chromatographic peak  area  (excluding  the  desorption solvent peak)
using one of the  procedures  described in Subsection  3-4.1.  Adequate resolution of
sample peaks  will only be  necessary in the chromatographic region(s)  where the
target compound(s) are expected to elute.  The GC analysis conditions and/or column
can be changed to achieve adequate  resolution.   The use  of  two different columns
may be necessary  to  ensure accurate identification of  the gases.   For analysis of
more  than  one  target  compound in  very complex  sample  matrices,  more  than one
analysis using different GC conditions  and/or columns may be  required to achieve
adequate resolution  for all target compounds.
     For analysis of flask samples  or bag samples,  (!)  use cylinder gases directly
(if available)  or by dilution  following the procedures  described  in Subsection
5-1.1 and  5-1.2,  respectively, or  (2)  prepare standards  in  Tedlar bags following
the procedure described  in Subsection 5-1-3  for  gaseous materials or the procedure
described in  Subsection 5-1-4  for liquid materials.   For analysis  of adsorption
tube samples,  prepare calibration  standards  following the procedure  described in
Subsection 5-1-6.    Data  forms should be used for recording calibration standard
preparation and analysis data  (see  Figures 5-4,  5-6, 5-8,  and 5-9) and preliminary
survey sample analysis data (see Figure 5-1)-
     The gaseous calibration standards for bag samples  must be injected into the GC
using a  gas  sampling valve equipped  with a  stainless  steel  or  Teflon sample loop
following the procedures described in Subsection 5-1  appropriate for the particular
type of  gaseous standard used.   Liquid calibration  standards  for adsorption tube
analysis must be injected into a heated sample injection port  following the proced-
ure described  in  Subsection  5-1-6.   The gaseous standards  for  glass  flask samples
can be   injected  into  the  GC using  either  a  gas  sample  valve,  following  the
appropriate procedure in Subsection 5-1 for  the particular gaseous standard used,
or  a  heated  injection   port  using  a gas  tight syringe  following the  procedure
described below;  the same injection procedure used for the standards  must be used
for the flask samples.
     The procedure for  injecting gaseous calibration  standards using  a  gas tight
syringe is  as follows:
     1.    Attach a GC septum  to a piece of Teflon tubing  and attach  the tubing to
          the outlet of  the calibration  gas  cylinder regulators  or the Tedlar bags
          containing the calibration gases.
     2.    Insert the needle of the syringe through the  septum, and repeatedly purge
          the syringe by repeatedly filling and emptying the syringe 7 times.
     3.    After purging  the  syringe,  fill the syringe past the  mark  corresponding
          to the  desired amount to be injected,  and withdraw the  syringe from the
          septum.   Stick the  needle  into a  rubber  stopper  or  a thick  septum  to
          prevent dilution of the standard by ambient air.
     4.    Immediately before  injecting  the  standard,  remove   the  needle  from  the
          stopper or  septum,  adjust the syringe to the desired  volume,  and inject
          the standard into the heated injection port on the  GC.   Note the time of
          injection on the strip chart and/or actuate the electronic integrator.
     5.    Repeat the injection  of  the standard until the  peak  areas  from consecu-
          tive injections agree within 5# of  their average  value.
o
 o

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                                                                 Section No. 3.16.3
                                                                 Date June 30, 1988
                                                                 Page 15

     Perform initial tests using the calibration standards to determine the optimum
GC  conditions  to minimize analysis time while still maintaining sufficient resolu-
tion.  Sufficient resolution can be determined following the procedure described by
Knoll42  or in EPA  Method 625A/* where the baseline  to valley height  between two
adjacent peaks must be less than 25% of the sum of the two peak heights (see Figure
3-3).
     Analyze  the calibration  standards,  starting  with the  lowest concentrations
first.   Repeat each standard analysis until  two  consecutive injections give indi-
vidual  area counts within 5#  of  their average.   Multiply the average of the re-
sponse for  the two acceptable consecutive injections of each standard by the detec-
tor attenuation  to determine  the calibration  area value for each standard.  Record
the retention  time for each  compound  and the calibration area  for each standard.
Record  the detector  settings,   the  recorder/integrator  attenuation  for  each
standard, the chart speed, the GC temperature settings, the column parameters (type
and length),  and the carrier gas  flow rate.   Plot the concentration of  the stan-
dards on  the  abscissa (x-axis) and  the  calibration area for each  standard on the
ordinate.   Perform a regression analysis,  and  draw the least squares  line on the
plot.   It  is recommended,  but  not  required  for  preliminary survey sample analysis,
that the  validity of the  calibration  curve be  checked using the  audit procedures
described in Section 8.0.  The audit sample may be analyzed at this time in lieu of
analysis  during the  final  sample   analysis  with   the  prior  approval  of  the
Administrator.
     If positive  identification of a target compound cannot be made by comparison
of the compound retention  time to  the  retention time  of one of  the standards,  then
use of a different type of column may be helpful.   If positive identification still
cannot be achieved, then  GC/mass spectrometry (GC/MS)  or  GC/infrared (GC/IR)  tech-
niques should  be used, with  GC/MS recommended.   In  addition,  any  compounds,  not
identified as target compounds, with peak areas greater than 5# of the  total chro-
matographable  peak  area  (excluding  the  solvent  peak area  for adsorption  tubes)
should be identified by comparison to known standards  or by using GC/MS.

3.4.2  Glass  Flask Preliminary Sample Analysis -  Since glass sampling flasks  are
only used for  preliminary survey  samples,  the analysis of the flasks is  described
in this section.   Glass sampling flasks require  some pressurization prior  to analy-
sis to withdraw the sample.
     Using  the ideal  gas law, the  amount of dilution  of  the sample that  results
from pressurization can be estimated with enough  accuracy  to permit interpretation
of the preliminary survey sample  results.   The  procedure for pressurizing  a  flask
is as  follows:
     1.    Note if any condensation has  collected in the flask.   If it has,  heat the
          flask to the flue gas or duct temperature with an  oven,  heating tape,  or
          a heat  lamp.    Note;  The  pressurization  of sealed glass containers  by
          heating is  an  inherently  hazardous process.   The use  of a protective
          shield  to  protect  personnel  from  flying  glass  in  the  event  of  an
          explosion is  highly  recommended.   In  addition,   the  flask  should  be
          wrapped in  cloth or  other cushioning media during these  operations.
    2.    Connect one end of the flask to a mercury manometer,  open  the  stopcock,
          and  determine the initial pressure of the flask  (Pi).   Record Pi  and  the
          initial absolute flask temperature (Tj)  in °R or  °K.
    3.    Connect the  other end of  the  flask to  a  source of hydrocarbon-free nitro-
          gen  or  air,  and open the  stopcock.  Slowly pressurize  the  flask to  a
          maximum of  15 psig,  and close the  stopcock.   Determine the final  pressure
          of the flask (Pf) and the  final absolute temperature  of the flask  (Tx).

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                                                                              1
                                           w
                                           v
             Figure 3-3-  Diagram  showing EPA Method 625 criterion for adequate  resolution of
                          overlapping compounds with similar mass spectra.
O
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                                                        CD p CD
                                                        Oq rt O
                                                        CD CD ct
                                                            H-
                                                        M C_| O
                                                        cr>c 3

                                                          CD Z
                                                            O
                                                          UJ •
                                                          O
                                                          VO (T>
                                                          03-
                                                          OOUO
O

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                                                                 Section No. 3-16.3
                                                                 Date June 30, 1988
                                                                 Page 1?

          Note;  The  pressurization  of  sealed glass  containers  is  an inherently
          hazardous  process.   The use of  a protective shield to protect personnel
          from  flying glass in  the event of an explosion is highly recommended.  In
          addition,  the  flask should be wrapped in cloth or other cushioning media
          during  these operations.
          Calculate  the  first dilution factor  (Dj) using the following  formula:
                                   Di =
                                         P  x T
                                         rf x ij
                                         T  x
                                         i  x
Equation 3-2
     5-   Allow  the  flask to equilibrate for 10 minutes.  Note if any condensation
          has formed. If  condensation has formed in the  flask and the flask did not
          initially  required heating, heat the  flask to  a temperature sufficient to
          vaporize the condensate.  If  the condensate cannot be vaporized or if the
          flask  was  already heated  and more condensate formed during pressuriza-
          tion,  the  sample cannot be analyzed accurately.
     6.   Close  the  stopcocks and disconnect the manometer and dilution gas.
     Analyze the contents of a pressurized flask using a sample introduced into the
GC via a gas sampling valve  by the following procedure:
     1.   Connect  the  sample flask  to the injection valve  with the valve  in the
          load position.
     2.   Open  the stopcock connected  to the  valve, and allow the  gas  sample to
          flow  through  the  sample  loop at 100 ml/min   for  30  seconds (determined
          with  a rotameter  connected  to the outlet of  the sample  loop)  or purge
          with 5 times the sample  loop volume,  whichever is less.   Close the stop-
          cock,  and  allow the sample loop to return to ambient pressure.
     3.   Actuate  the  sample valve to  inject  the sample and  record the injection
          time.
     4.   Examine  the  chromatogram and determine  if adequate  resolution  has been
          achieved between  individual  target  compound  peaks  and  between  target
          compound peaks  and any  interfering  compound  peak with an  area greater
          than 5# of the  total area  of all  peaks (excluding the desorption solvent
          peak) using the procedure described in Subsection 3-4.1.
     5.   Determine  the retention  time for each  peak  by dividing  the  distance of
          the peak maximum from the injection point by the chart speed.
     6.   Repeat the analysis, and determine the peak area  and retention time for
          each target compound identified during the second analysis.  Although not
          required for the preliminary survey sample analysis, the  peak  areas for
          each target compound  from consecutive injections  should  agree  within 5%
          of the average peak area.  The retention times between the two injections
          should agree  within 0.5  seconds or  1% of the adjusted  retention time
          (compound  retention time minus  the  time  of elution of unretained peaks),
          whichever is greater.
     Analyze the contents of a pressurized flask using a sample introduced into the
GC via  a gas tight  syringe  and a heated injection port sample by  the  following
procedure:
     1.    Attach a GC septum to one of the  stopcocks  on the glass  flask.   (Note:
          Glass sampling flasks can be purchased with an integral septum porti)
     2    Insert the needle  of the syringe through  the  septum, and purge  the sy-
          ringe by repeatedly filling and emptying the  syringe 7 times.
     3.    After purging the  syringe,  fill the  syringe past  the mark corresponding
          to the desired  amount  to be injected, and withdraw the syringe  from the

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                                                                                      o
                                                                 Section No. 3.16.3
                                                                 Date June 30, 1988
                                                                 Page 18

           septum.   Stick  the needle into  a rubber  stopper or a  thick  septum to
           prevent  dilution of the  standard by ambient air.
     4.    Immediately  before  injecting  the  sample,  remove  the  needle  from the
           stopper  or septum,  adjust  the syringe  down  to the  desired  volume, and
           inject  the sample  into  the heated injection  port on the GC.   Note the
           injection  time on  the strip chart and/or actuate  the electronic integra-
           tor.
     5.    Determine  the retention time  for  each peak by  dividing the distance of
           the peak maximum from  the injection point by the chart speed.
     6.    Repeat  the  analysis,  and determine the retention  times for each peak for
           the second analysis.   The retention times of successive injections should
           agree  within  0.5   seconds  or  within 1%  of  the  mean  of  the  adjusted
           retention times, whichever  is  greater.

3.4.3  Analysis of Preliminary Survey Bag Samples  - Follow the procedures described
in  Subsection  5-3-1  for the  analysis of bag samples.   To assess  the stability of
the gas sample in  Tedlar bags, perform a second  analysis after a time period equal-
ling the  period  between sample collection and  the first analysis.   If the concen-
tration of the sample  collected in a Tedlar bag decreases by more than 1Q% between
the first and  second analysis,  then  an  accepted sampling method other than Tedlar
bags should be considered.
     Perform a retention check on  the bag sample by successively evacuating the bag
and refilling it  with  hydrocarbon-free  air  or nitrogen one or more times.  Analyze    -^
the bag  contents  for  the target compound(s),  allow the  gas to  sit in  the bag   f   j
overnight,  and  reanalyze bag contents  for  the  target compound(s).   If any target   V.	J
compound  is detected in the  bag at a concentration greater  than 5# of the original
concentration, then  an  accepted sampling method other  than Tedlar  bags  should be
considered.

3.4.5  Analysts of Preliminary Survey Adsorption Tube Samples - Follow the proced-
ures described in  Subsection 5-3-4 for  the  analysis of adsorption tube samples.  A
minimum desorption efficiency of $0% must be obtained.   If  $0% desorption effici-
ency cannot be achieved using the  referenced procedures  from Table B in the Method
Highlights  Section,  then  try longer desorption  times,  more  vigorous  desorption
techniques  and/or  other desorption solvents.   If $0% desorption  efficiency still
cannot  be accomplished,  then an  accepted  sampling  method  other  than  adsorption
tubes should be considered.

3.4.6   Interpretation  of Preliminary Survey Eesults  - To  select  the most suitable
sampling and analytical method for the final field test,  the results of the prelim-
inary survey must  be properly interpreted.   The major points  to  consider are (1)
the sampling location,  (2) the parameters of the process being tested,  (3)  the flue
gas moisture and temperature and the flue or duct static pressure,  (4)  stability of
the gas sample in  bags,  (5)  the  desorption efficiency of the target compounds from
adsorption tubes,   and  (6)  the resolving  capability,  precision,  accuracy,  and speed
of  the  GC  analysis.    Thus,  flue gas  or duct  parameters  and components  present
determine which sampling and analytical  methodologies will be the most appropriate.
     Sampling Location  - The  hazards  associated with  the sampling  location  will
influence the type  of sampling methodology which can  be used.   In  explosion  risk
areas where use of  pumps,  heated probes,  or a GC with  a flame ionization detector
(FID) would be prohibited,  the explosion  risk area sampling procedure  can  be  used
safely.  Close attention must be paid  to maintaining the proper sampling rate  when
                                                                                       o

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                                                                 Section No.  3.16.3
                                                                 Date June  30,  1988
                                                                 Page 19

 using the evacuated  canister  as a vacuum  source.   It may  be possible at certain
 hazardous  locations,  to locate  the collection device  {bag  or adsorption tube)  in
 the  explosion risk area near  the source  and operate the sampling pump a safe  dis-
 tance away.    Also,  intrinsically safe personnel  sampling pumps could be  used  in
 certain  hazardous areas  provided  the  required sampling rate can  be maintained.
 Hazardous  sampling locations may not be  suitable  for direct or dilution interface
 sampling when using an electrically-heated  probe and sample  line.
      Other physical  factors concerning  the sampling location will  also influence
 which sampling method is most suitable.   These factors  will be site-specific and
 are  beyond the scope  of this Handbook.

      Process  Parameters  -  The  particular  process parameters  pertaining to  the
 generation of  the organic  emissions  and  the  effect  the   operation  has on  the
 emission levels  will  influence which sampling technique will be most suitable.    In
 the  case  of  a continuous process where emission levels  are constant,  each of the
 Method  18 sampling  techniques  should  be  suitable with  regard  to  the  process
 parameters.   For processes operating in a batch or cyclic mode, the bag or adsorp-
 tion tube integrated sampling  techniques  may  be  more  suitable  compared to  the
 interface  techniques where grab  samples are analyzed.

      Flue  Gas or Duct Conditions -  The flue gas or duct moisture and temperature
 will have a  major influence  on selecting  the  most suitable sampling technique.
 High moisture  will affect both bag samples  and adsorption tube samples.  For situa-
 tions where  moisture may be  a  problem,  the interface  techniques  are recommended
 provided the 5%  criteria for consecutive injections, described in Subsections 5-3-2
 and  5-3-^» can be met.  Condensation in bag samples may result in the target organ-
 ic  compounds   being  absorbed  into  the  condensate,  or,  at  extremely  high  concen-
 trations,  being  the  condensate  itself.   The heated bag  sampling  technique may  be
 suitable provided on-site analysis is  conducted when it is  not practical  to keep
 the  bags  heated  until analysis  at  the  base laboratory.  Condensation  may  also  be
 avoided by using a diluted bag sample collected by prefilling the bag with a known
 quantity  of   hydrocarbon-free  air  or nitrogen  prior  to  sampling  and accurately
 metering the gas sample into the bag during sampling.
      Moisture  reduces the adsorptive  capacity of certain types of adsorbents (pri-
 marily  charcoal).  .  For  sampling with  adsorption  tubes  at   sources  with  moisture
 above 3%,  a  silica  gel  tube  may be inserted in  front of  the  primary adsorption
 tube; otherwise,  two  or  more  adsorption tubes connected  in  series  should  be used.
 The  first tube  becomes  a  sacrificial tube and should be  positioned vertically
 during sampling.  A disadvantage of this approach is that the additional tubes will
 also  require  analysis.    Alternatively,  a  moisture knock-out  jar  can be  used  in
 front of  the   adsorption tube.   As varying amounts of the  organic  emissions will
 also  condense  (the amount of each organic  removed  from  the  gas stream will largely
 depend on  the  individual compound's volatility and solubility characteristics),  the
 liquid collected must be  retained for analysis.  Accurate quantitation of  various
 organics in  the  condensed  liquid(s) may  involve  several steps  and is  generally
 problematic.
     The flue gas temperature may also dictate which sampling technique can be used
 due to limitations of the sampling equipment.

     Bag Sample  Stability and Target Compound "Retention -  If on-site  analysis of
bag samples is not feasible  and the  samples are returned to  the base  laboratory  for
 analysis,   then the stability  of the gas sample in the bag  will  be a factor  and
should be determined.  While the stability  of organics  in bags has been demonstra-

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                                                                 Section No. 3.16.3
                                                                 Date June 30, 1988
                                                                 Page 20

ted in numerous laboratory evaluations, an actual source sample could contain other
unknown  components  which may affect  sample  stability.   If  the preliminary survey
sample analysis indicates that the gas sample is not stable, then one of the alter-
native sampling  procedures should be used.   The  check should be  conducted  at an
elevated temperature if the bag is to be heated during sampling.
     The retention of  the  target  compounds by  the  Tedlar bag should also be check-
ed.   This  check  will  indicate  any  sample  loss not  determined by  the stability
check.   If the retention  of a target compound  by the Tedlar  bag  is unacceptably
high, then  the bag sampling  technique is  not suitable  for that target compound and
one  of  the alternative  sampling procedures should  be used.   Heating  of  the bag
during sampling and analysis may reduce the retention.

     Adsorption Tube Desorption  Efficiency - The  desorption efficiency determined
for  the  adsorption  tubes must be >50#.    If >50%  desorption efficiency cannot be
achieved with  the referenced procedure,  then  more vigorous  desorption techniques
and/or solvents should be  evaluated.   The desorption efficiency,  as determined by
the procedures described in  Subsection 5-1.6,  will not indicate if the gas sample
matrix  will  affect   the  desorption  of  the   target   compounds.    If  acceptable
desorption  efficiency  cannot be achieved,  then one of  the alternative  sampling
procedures  should be  used.  Also,  the adsorption  efficiency must  be  greater than
90#. The breakthrough volume must not be exceeded.

     Calibration Standards and GC Analysts - The availability of calibration stan-
dards may dictate which sampling technique can be used.  The GC analysis may also
dictate which sampling technique will be the most suitable.   For accurate analysis,
adequate  resolution  must  be achieved between  target  compounds  and  between any
interfering  compounds   and  target  compounds.    During  preliminary survey sample
analysis, acceptable resolution  may not be  achievable  on a gas sample but may be
accomplished with the  adsorption tube sample,  or  vice versa.   Thus,  the sampling
technique which gives  acceptable  resolution  during sample analysis must be select-
ed.  In some situations where analysis of more than one target compound is requir-
ed,  two  or  more  analyses of the  same sample under different GC conditions and/or
with different columns may be necessary to achieve  adequate  resolution.
     Acceptable accuracy,  as demonstrated by  audit  sample  analysis,  must  also be
achieved for sample analysis by either gas or liquid injection.   Again the sampling
technique that gives acceptable  accuracy during sample analysis must  be selected.
The sampling technique that gives acceptable precision,  as demonstrated by consecu-
tive replicate injections,  must be selected.   Minimizing  the analysis  time is par-
ticularly important for  the  interface techniques.   As  discussed above,  the preci-
sion limits may be hard to achieve with the interface techniques with a long analy-
sis time under variable or cyclic emission conditions.

3-5  Apparatus Check and Calibration

     Figure 3-4 summarizes the pretest apparatus checks and  calibration and can be
used as  a  pretest  operations  checklist.   Figure  3-5  can  serve  as  an equipment
packing list and status report form.

3.5-1  Probe - If a heated probe is  required for  the selected  sampling procedure,
then the probe's  heating system should be checked to see that it is operating prop-
erly.  The  probe should be  cleaned internally by  brushing  first with  tap water,
then with deionized distilled water, and finally, with acetone.   Allow  the  probe to
air dry,  then the probe should  be heated  and  purged with air  or  nitrogen.  The
o
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 o

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                                                                 Section No. 3-16.3
                                                                 Date June 30, 1988
                                                                 Page 21

 Date 	  Calibrated by	

 Check Sampling Technique To Be Used

 Direct Bag 	, Dilution Bag 	, Direct Interface 	, Dilution Interface 	,
 or Adsorption Tube 	.

 Sampling Checks  (Check only applicable methods)

 Velocity and Water Vapor Content

 Pitot tube dimension specifications checked?	yes 	no   (specification of Method
 2,  Handbook Section 3.1)

 Differential pressure gauge pretest calibration acceptable? 	yes 	no 	N/A
 (specifications of Method 2, Handbook Section 3.2)

 Stack temperature sensor calibrated against a reference thermometer?* 	yes 	no
 (within 5°F of reference thermometer)

 Barometer  pretest field barometer reading correct?  	yes 	no (within 2.5 nua
 (0.1  in.)  Hg of the mercury-in-glass barometer)

 Wet bulb/dry bulb thermometers accuracy acceptable?  	yes 	no  (within 1°F of
 true  value, manufacturer's specifications)

 Method 4 sampling equipment acceptable?* 	yes 	no (Handbook Section 3.3, PRE
 TEST  SAMPLING CHECKS, Method 4, Figure 2.5)

 Direct Bag

 Pretest calibration of flowmeter acceptable?  	yes 	no (within 10 percent of
 0.5 liter/min for single check)

 For heated box system, pretest calibration of the temperature sensor in the box is
 acceptable?  	yes 	no 	N/A (within 5 percent of reference value at
 temperature of expected use)

 Dilution Bag

 Pretest calibration of flowmeter acceptable?  	yes 	no (within 3 percent of wet
 test meter)

Pretest calibration factor of dry gas meter acceptable?   	yes 	no (within 2
percent of wet test meter)  	


*Most significant items/parameters to be checked.

 (Continued)
                      Figure 3-4.  Pretest sampling checks.

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                                                                 Section No. 3.16.3
                                                                 Date June 30, 1988
                                                                 Page 22

Figure 3.4  (Continued)

Direct Interface and Dilution Interface

Pretest calibration of stack temperature sensor acceptable?*  	yes 	no (within
2°F of reference value)

Pretest calibration of probe and heated sample line temperature sensor acceptable?*
	yes 	no (within 2°F of reference value)

For dilution interface only, pretest calibration of dilution system acceptable?*
	yes 	no (within 10 percent of expected dilution factor)

Pretest calibration of gas chromatograph acceptable?*	yes 	no (specifications
shown in POSTSAMPLING OPERATIONS CHECKLIST, Figure 5.10)

Adsorption Tubes

Pretest calibration of limiting orifice acceptable?*	yes 	no (compared to
bubble meter)

*Most significant items/parameters to be checked.
                                                                                       o
                                                                                       o
                                                  '.- \ V
                                                 I;  ' '

-------
                                                                  Section No. 3.16.3
                                                                  Date June  30, 1988
                                                                  Page 23
Apparatus check
Moisture Determination
V Bulb/D Bulb
Checked
Barometer
Calibrated*
Method 4
Probe, heated &
leak checked
Impingers
Meter system
calibrated*
Velocity Determination
Pitot Tube
Number
Length
Pressure Gauge
Manometer
Other
Stack Thermometer
Calibrated

Bag Sampling
Probe Liner
S steel
Glass
Teflon tube
Length
Meter System
Flowmeter*
Pump
Evacuated can
Charcoa I tube
Sample line
Tedlar Bags
Number
Blank checked
Heated Box
Number
Heat checked
Acceptable
Yes



No



Quantity
Required



Ready
Yes



No



Loaded and Packed
Yes



No



*Most significant items/parameters to be checked.

                        Figure 3-5-  Pretest preparations.

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                                                                 Section No. 3-16.3
                                                                 Date June 30, 1988
                                                                 Page 24
Figure 3.5  (Continued)
o
Apparatus check
Bag Sampling (continued)
Dilution
Inert gas
Meter
Gas Chromatograph
On-site
(check below)
N/A

Direct or Dilution
Interface
Probe Liner
Glass
S steel
Teflon
Heated Line
Length
Heat checked
Temperature Sensors
Stack
Probe
-Calibrated*
Sample Pump
Dilution System
Dilution pumps 	
Flowmeters
Dilution gas
Heated box
Dilution factor
checked*
Gas Chromatograph
(shown below)
Adsorption Tube
Probe
Heated
Checked
Nonheated
Glass
S steel
Filter
Acceptable
Yes



No



Quantity
Required



Ready
Yes



No



Loaded and Packed
Yes



No



                                                                                       O
*Most significant items/parameters to be checked.
                                                                                       O

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                                                                 Section No. 3.16.3
                                                                 Date June 30,  1988
                                                                 Page 25
Figure  3.5   (Continued)
Apparatus Check
Adsorption Tube (continued)
Sample Line
Type
Length
Checked*
Pump and Meters
Pump
Orifice
Calibrated*
Eotameter
Calibrated*
Timer
Adsorption Tubes
Type

Gas Chromatograph
Cylinder Standards
Analyte
PPM
PPM
Regulators
Bags
Size
Dilution system
Calibrated*
Diluent gas
Bag Standards
Analyte
Syringes
Iwptnger/hot
plate assembly 	
Gas meter
N2 gas
Regulator
Bags
Size
Other Gases
Fuel
Carrier
Zero
Columns
Type
Acceptable
Yes


No


Quantity
Required


Ready
Yes


No


Loaded and Packed
Yes


No


*Most significant items/parameters to be checked.

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                                                                 Section No.  3.16.3
                                                                 Date  June 30,  1988
                                                                 Page  26
Figure 3.5  (Continued)
Apparatus Check
Gas Chromatograph
Type
Temp /con oven

Bulk Samples
Bottles
Type
Size
Acceptable
Yes


No


Quantity
Required


Ready
Yes


No


Loaded and Packed
Yes


No


o
 *Most significant items/parameters to be checked.
                                                                                      O
                                                                                      o

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                                                                  Section No. 3-16.3
                                                                  Date June 30,  1988
                                                                  Page 27

 probe should be sealed at the inlet end and checked  for leaks by applying a vacuum
 of 10 in. H20.  See  Subsection  1.0 for the probe leak check procedure.  The probe
 is considered leakfree under these conditions if no  loss  of vacuum is seen after
 one minute.   Any leaks should be corrected or the probe should be  rejected. If the
 probe has an external sheath, the integrity of the seal between  the sheath and the
 probe liner  should be checked to ensure ambient  air does not dilute the gas sample.

 3. 5 -2  Teflon Tubing  - Prepare  enough sections  of tubing for connecting the probe
 to bag or tube samples.

 3.5.3  Quick  Connects or Equivalent  - The quick connects,  or  their  equivalents,
 should be new or cleaned according  to the manufacturer's  recommendations.    Leak
 check the quick connects  as  described  in Subsection 1.0.

 3.5.4  Barometer -  The field barometer should be  compared with the  mercury-in-glass
 barometer or with  a  National Weather Service Station  reading prior to each field
 test.
 3.5.5   Met Bulb/Dry Bulb  Thermometers  -  For sources with stack temperatures below
 59° C  where wet  bulb/dry  bulb thermometers  will be  used to  determine  stack gas
 moisture  content,  the  thermometers should  be compared  with the mercury-in-glass
 thermometer at room temperature prior to  each field  trip.

 3.5.6   Method 4  Equipment -  Where Method 4  will  be used  to  determine  stack gas
 moisture  content,  prepare the  equipment  for sampling  following  the procedures
 described in Section 3-3.3 of  this  Handbook.

 3.5.7  S-type Pitot Tube and Differential Pressure Gauge  - Prepare the S-type pi tot
 tube and the differential  pressure gauge for sampling following the procedures de-
 scribed in Section  3-1.3 of this Handbook.

 3.5.8  Sampling  Pump - Check  the sampling pump for delivery rate and leaks before
 going  to  the field as follows:   Attach a  0  to  5 liter/minute rotameter, to the
 outlet of  the  pump  and turn  on the pump.    Check  the flow  rate indicated by the
 rotameter.   Reject  or  repair  the pump if the flow rate is not at least 1 liter/mi-
 nute.  If the flow  is adequate, then conduct  a  leak  check by plugging the inlet of
 the pump.  If  the pump is leak free then the rotameter should eventually indicate
 no flow.  Repair or replace the pump if a leak  is indicated.

 3.5.9  Tedlar Bags  - Prepare new Tedlar bags  for sampling by leak checking the bags
 before going to  the field.  The bags should also be  checked for contamination by
 filling with hydrocarbon- free  air or nitrogen during the  leak check.  The bags are
 checked as follows:  Connect  a water manometer,  or equivalent, using a  tee con-
 nector between the  check valve quick connect on  the bag  and a pressure source (or
 hydrocarbon-free  air  or nitrogen for  conducting the  contamination  check) .   Pres-
 surize the bag  to 5 to 10 cm (2 to 4  in.)  H20 and disconnect the  quick connect.
 Loss of pressure  over  a 10 minute  period indicates a leak.   Alternatively, leave
 the bag pressurized overnight; a deflated bag the following day is  indicative of a
 leak.  Reject  or repair any  bags  with leaks.   After the hydrocarbon- free  air or
 nitrogen has  remained in the bag for 24  hours,  analyze the bag contents using a GC
with a flame ionization detector on the most sensitive setting.  The bag should be
rejected if any organic compounds are detected that may interfere with the analysis
of any of the target compound (s) .

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                                                                 Section No.  3.16.3
                                                                 Date June 30,  1988
                                                                 Page 28

3.5.10   Etgtd Leak-Proof  Containers - The  rigid containers  used to  contain  the
Tedlar  bags  during  sampling  should be  checked for  leaks prior  to going  to  the
field.   The  container  should  be leak checked  with the  bag  in place  as follows:
Connect a water manometer, or  equivalent, using a  tee  connector between a pressure
source  and the container outlet.  Pressurize the  container to 5 to 10  cm  (2  to 4
in.) Hg.  Any loss of pressure after 10 minutes indicates a leak.  Reject or repair
the rigid container if a leak is indicated.

3.5-11  Direct Pump Sampling System - If the direct pump sampling system is select-
ed, then  the system  should  be  assembled and  leak checked prior  to going  to  the
field as follows:  Assemble the  system  (see  Figure 4.5).   Attach a vacuum line and
a  rotameter  to the  inlet  quick connect.   Plug the  probe inlet  and turn  on  the
vacuum  pump.   If  the system is leakfree up  to  the  pump, the rotameter should even-
tually  indicate no flow.  An alternate procedure to leak check the system up to the
male inlet check  valve  quick connect is as  follows:   Connect a water manometer, or
equivalent, using a  tee connector between a pressure  source and  the  inlet  end of
the probe.   Pressurize  the system to 5  to  10 cm  (2  to 4 in.)  Hg.   Any  loss of
pressure after 30 seconds  indicates  a leak.   Reject or repair the sampling system
if  a  leak  is indicated.   Check to see if  the pump is  contaminating  the sampling
system  by filling a  second contamination-free  Tedlar  bag with hydrocarbon-free air
or  nitrogen,  and  with the  system assembled pull the hydrocarbon-free  air or nitr-
ogen from the second  Tedlar bag  into the  first  Tedlar  bag using the pump.  Analyze
the first  bag contents  using  a GC with  a  flame  ionization  detector on  the  most
sensitive setting.   The pump  should be rejected or repaired,  cleaned,  and checked
again if any organic compounds are detected that may interfere with the analysis of
any of  the target compound(s).

3.5.12  Needle Valve and Rotameter - Prior to each field trip or at sign of erratic
behavior, the flow control valve and the rotameter should  be  cleaned  according to
the maintenance procedure recommended by the manufacturer.

3.5-13  Teflon Probe - For bag  sampling  in  an explosion risk area, prepare a  new
Teflon  probe  or   clean  a used Teflon  probe following  the procedure  described in
Subsection 3•5•1 -   Leak check the Teflon probe as follows: Attach a mercury manome-
ter, with a tee connector, and a vacuum pump to the outlet of the  probe.  Plug the
inlet end of  the  probe and apply a vacuum of  10 in.  H20.  The  probe is considered
leak free under  these conditions if no  loss of vacuum is seen after  one  minute.
Any leaks should  be corrected or the probe should be rejected.

3-5-14   Explosion Risk  Area  Sampling System  - The explosion risk area sampling
system  should be  leak checked  as follows:  Evacuate the  steel  drum.   Assemble  the
system  (see Figure 4.6), with the pinch clamp open, the sample bag leak checked and
evacuated,  and directional needle valve closed.  Attach a mercury  manometer to  the
inlet of the  Teflon probe.   Open the needle valve.   The rotameter should eventually
indicate no flow.  Once there  is no flow, note the manometer  reading.   The system
is  considered leak free  under  these  conditions if no loss  of  vacuum is seen after
one minute.   Any  leaks should be corrected or the system should be rejected.   It is
recommended that  an  explosion-proof  pump  be used  in  the explosion risk  area or a
regular pump be used outside  the risk area.   Follow the  procedures  described  for
these pumps.

3-5-15  Heated Bag Sample Container and Sample Lines -  If other modified bag sampl-
ing techniques are selected due  to  condensation observed  during  sampling,  heated
o
o
 o

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                                                                 Section No. 3-16.3
                                                                 Date June 30, 1988
                                                                 Page 29

 bag sample containers and  sample  lines  will be required.   The heating systems of
 this equipment should be checked prior  to going to  the  field to see that they are
 operating properly.   The sample lines  should  be cleaned  following the procedure
 described for the sampling probe in Subsection 3-5.1.   The heated sampling system
 should be  assembled and  leak checked  prior to  going  to  the field  as follows:
 Assemble  the  system (see Figure 4.5).   Attach a vacuum pump and a rotameter to the
 inlet quick connect.  Plug the probe inlet  and  turn on the vacuum  pump.   If the
 system is leak free, the rotameter should eventually indicate  no  flow.  An alter-
 nate procedure to leak check the system up  to  the female outlet check valve quick
 connect on the bag container is as follows:   Connect a water manometer, or equiva-
 lent,  using a  tee connector between  a  pressure  source  and the inlet  end  of the
 probe.  Pressurize the system to 5 to 10 cm (2 to 4 in.) Hg.  Any loss of pressure
 after 30  seconds  indicates  a leak.   Reject or repair the sampling system if a leak
 is  indicated.

 3.5.16  Direct Interface Sampling System  -  The  heating  system of the sampling
 probe should  be  checked prior  to  going to  the  field  if heating  is  required to
 maintain  the  gas  sample  above the duct temperature and/or to prevent condensation.
 The probe  should also be  cleaned and leak checked following  the procedures describ-
 ed  in Subsection  3«5-l.   If the probe has an external sheath, the integrity of the
 seal between  the sheath and  the probe  liner should be checked to ensure ambient air
 does not  dilute the gas  sample.   The sample line should be cleaned following the
 procedure  described  for the sampling probe in Subsection 3-5.1.  The heating system
 of  the sample line should be  checked  before going to the  field to  see that it is
 operating  properly.   The direct interface sampling  system should  be assembled and
 leak checked  prior  to going to the  field as follows:   Assemble the  system (see
 Figure  4.5).   Switch the gas  sampling valve to the  inject  position,  and plug the
 outlet  from the sample valve.   Connect  a water manometer,  or  equivalent,  using a
 tee  connector between a pressure source  and the inlet end of the probe.  Pressurize
 the  system to 5 to 10 cm (2  to  4  in.) Hg.   Any loss  of pressure  after 30 seconds
 indicates a leak.   Reject or repair the  sampling system if a leak is indicated.

 3.5-17  Dilution  Interface Sampling System  - The equipment required for dilution
 interface  sampling is  the same  as  required  for  direct interface sampling, with the
 addition of a heated dilution  system and a  larger heated sample pump.  The heating
 systems should  be  checked to see that they are operating properly.   Prior to each
 field trip or at sign of erratic behavior, all flowmeters should be cleaned accord-
 ing  to  the maintenance procedure recommended by the  manufacturer.   The flowmeters
 should  also be  calibrated following the procedures described  in Subsection 2.1-3-
The dilution interface sampling system should also be checked for leaks as follows:
Assemble the  system (see Figure 4.6).   Connect a water  manometer,  or equivalent,
using  a tee connector between  a pressure source and  the inlet end  of the probe.
Plug  the  three outlet vents  to  the charcoal adsorbers  and the outlet  of  the two
 flowmeters.   Pressurize  the system to 5 to 10 cm  (2 to  4  in.)  Hg.   Any  loss of
pressure after 30 seconds indicates a  leak.   Reject  or repair the system if a leak
 is indicated.   It is advisable to verify the operation of the dilution system prior
 to  going  to the field following the procedures described  in Subsections 4.3-7 and
5.3.3.

 3.5.18   Gas  Chromatography  System -  Refer to Table C  in the Method Highlights
Section to ensure  that the proper detector has been selected for the target organic
compounds.  Prior to taking  the gas Chromatography system to the field, check that
 all  systems are operating properly.   Consult the operator's manual  for procedures

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o
                                                                 Section No.  3-16.3
                                                                 Date  June  30,  1988
                                                                 Page  30

 to verify that the equipment is operating properly.   Check  to  see  that all  cylinder
 gas regulators,  connections,  and tubing are functioning  properly and are leak free.
 This is particularly  important when using hydrogen  and oxygen.   Consult  with  the
 regulator manufacturer for procedures on checking pressure  regulators.  Connections
 and tubing can be checked for leaks  by pressurizing with the gas and wetting  with  a
 soap solution or  other commercially available solutions.   Any bubbles forming on
 the connections indicate a leak.  Tighten or replace any leaking connections.  An
 alternative leak check procedure for carrier gas  is as follows:  Plug  the outlet of
 the analytical column.  Pressurize the tubing and connections.  Turn off the  cylin-
 der valve and note pressure  on the  regulator gauge and, if equipped,  the  GC pres-
 sure gauge.  Any  loss  of pressure indicates a leak.   Locate the leak  using  a soap
 solution or work backwards  through  the carrier gas flow  path disconnecting  each
 component and plugging the carrier  gas  flow until the  leak is located,  a similar
 check should be made  of the gas sampling valve, sample loop, and connections.
      It is advisable  to  take to the field an adequate supply of spare parts,  sep-
 tums,  different  size  sample loops, extra  analytical  columns, and  other related
 equipment that may fail or deteriorate during the emission  test.  The  generation of
 response factors  for  each target organic compound,  relative  to  a single organic
 compound,  should be confirmed  in  the laboratory  prior  to going to the field.   The
 confirmation procedure involving preparation and analysis of  calibration standards
 containing multiple organic compounds is described in Section  5.1.6.

 3.6  Reagents and Equipment

      The following reagents  and equipment may  be required  'to conduct  the  emission
 test depending on the sampling method selected.  These materials are  generally  ac-
 quired from commercial vendors.  Certification of purity and/or analysis should be
 obtained for adsorption tubes, calibration and zero gases,  and liquid  organic com-
 pounds .

 3.6.1   Charcoal Adsorber - Check to see  that  the supply of charcoal  adsorbent is
 sufficient to  last for the entire  field  test  period.

 3.6.2   Adsorption Tubes - If adsorption tube sampling is to be conducted,   check to
 see that the proper cype of tube has been obtained  for collecting the target or-
 ganic  compounds.   Refer  to Table B  in  the Methods Highlights  Section  to determine
 the proper p^sorption material.  Check  to see  that the  supply of adsorption tubes
 is suffi^ent  to  conduct the emission test, including field blanks and for desorp-
 ti™ efficiency determinations.

 3.6.4   GC Carrier Gas -  Check  the GC operator's  manual  and the GC column manufac-
 turer  to  see that the  GC carrier gas type and grade are compatible with the GC and
 the  column.  Check to  see that the supply of carrier  gas is sufficient to last the
 entire field test  period.

 3.6.4  Auxiliary  GC Gases - Check  to see if the proper  type and grade of auxiliary
 gases required by  the GC  detector have been obtained.   Consult with the GC detector
 manufacturer to  determine the proper  type and grade  of  auxiliary  gases  required.
Check  to  see that the  supply of auxiliary gases  is sufficient to  last the entire
 field test period.                                                                    x—x

3.6.5  Calibration Gases - Check to see if the correct calibration gases in the re-   V_x
quired range have been obtained.  If available,  commercial cylinder  gases may be
o

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                                                                 Section No.  3.16.3
                                                                 Date June  30,  1988
                                                                 Page 31

 used if their concentrations have been  certified by direct  analysis; cylinder gases
 with tighter tolerances on their concentrations are  preferred.   Check to  see  that
 the  supply of calibration  gases  is  sufficient  to last the entire field  test period.

 3.6.6  Calibration Gas  Dilution  System  - Prior to each field  trip or at the sign of
 erratic behavior,  any flow control  valves or rotameters used  in the dilution  system
 should  be cleaned according to  the maintenance procedure recommended by the manu-
 facturer.   The  rotameters or other metering  devices used with  a single-stage or
 two-stage dilution system  should be calibrated prior to going to the field follow-
,ing  the  procedures  described in  Subsection  2.2.    It is  advisable to  check the
 dilution ratio of the  dilution  system prior  to  going to  the  field following the
 procedures described  in Subsections 4.3.7 and  5-3-3-

 3.6.7   Zero  Gas - Check to see  that the zero  gas  meets the requirements for being
 hydrocarbon-free  (less  than 0.1  ppmv of organic material as propane or  carbon equi-
 valent) .  Check to see  that the  supply of zero gas is  sufficient to last the entire
 field test period.

 3.6.8  Audit Gases -  Check to see that the required audit gases in the proper range
 have  been acquired.   Consult  Table A  in  the  Method  Highlights Section  for audit
 gases available  from  the  EPA for the target organic  compounds.    The  availability
 and ranges of audit gases  can be determined by contacting:

         Environmental Protection Agency
         Environmental Monitoring Systems Laboratory
         Quality Assurance  Division  (MD-77B)
         Research Triangle  Park, North Carolina 27711
         Attention: Audit Cylinder Gas Coordinator

 For  audit gases  obtained  from a commercial gas manufacturer, check  that  the manu-
 facturer has  (1)  certified the gas in a manner similar to  the  procedure described
 in 40 CFR Part  61,  Appendix B, Method 106,  Section 5.2.3.1 and (2)  obtained an
 independent analysis  of the audit cylinder that verifies that the audit gas concen-
 tration  is within 5%  of the manufacturer's stated concentration.

 3.6.9  Organic Compounds for Preparing Gaseous Standards - If gaseous standards are
 to be prepared  in the field,  check to see if  the organic compounds  to  be used are
 at least 99-9# pure or, if less  than 99-9#»  of known purity necessary to calculate
 the gaseous standard  concentration.  Record  the manufacturer's  lot number for each
 standard compound.

 3.6.10   Equipment for  Preparing  Gaseous  Standards  by Liquid  or Gas Infection-
 Confirm  that the Tedlar bags to contain the gaseous standards have been leak check-
 ed following  the  procedures  described  in Subsection  3-5-9-    Check to  see that the
 syringes selected are gas-tight,  cover the range needed (1.0- to 10-microliters for
 liquids and 0.5 ml for gases),  and are accurate to within i%.   Confirm that the dry
gas  meter and  temperature gauge  have been   calibrated  following the procedures
described in Subsection 2.0.   Clean the midget impinger assembly with detergent and
 tap water, and then  rinse with  deionized  distilled  water.   Check the system  for
leaks as follows:   Assemble  the appropriate  system  for  preparing standards (see
Figure  5.5 for gaseous materials  or Figure 5.6  for  liquid  materials).    Fit  the
injection port with a new septum.   Fill the Tedlar bag and  pressurize the system
to 5 to  10 cm  (2  to 4 in.) Hg.  Any loss of pressure after 10 minutes  indicates  a

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                                                                 Section No.  3.16.3
                                                                 Date June 30,  1988
                                                                 Page 32               S~\

leak.  Reject or repair the system if a leak is indicated.

3.7  Packing Equipment for Shipment

     The packing techniques described in this section are not requirements, but are
suggestions based on  previous  field experience.   The type of  packaging for  equip-
ment going to the field depends  on  the  mode of transportation.  Typically, packing
equipment for  transport by  a  common carrier  will  require the greatest  degree of
effort  to  ensure the equipment  arrives on-site in  its original condition.   When
possible, delicate equipment should  be  packed in the original shipping containers.
For convenience, label all  containers with  the contents for  easy identification in
the field.  The most  common mode of packing will be in  a van or trailer, where the
equipment will remain during transport.  More sophisticated  test  firms have trai-
lers or trucks dedicated to the  type of sampling being  conducted.   These units are
often designed to allow the test equipment  and instruments to remain set up during
transport.  This approach  minimizes the time and effort  required  to set up  before
and breakdown after a test.  A dedicated test vehicle  provides a  working environ-
ment that greatly enhances the quality of work that can be performed.

3.7-1  Probe - Pack the probe in a rigid case protected by polyurethane foam, poly-
ethylene  bubble-pack, or  other  suitable  packing material.    Seal  the  inlet  and
outlet of the probe with  tape or other suitable material.   Protect any protruding
gloss ends from  breakage  by insertion  into rigid plastic pipe lined  with foam or
other packing material.

3.7-2   Teflon Tubing, Sample Lines,  and Vacuum Lines   -  All  tubing, sample  lines,
and vacuum lines  should be  coiled  and  secured with  tape.   Coils should  be large
enough not to crimp tubing or excessively strain the heat sheath.   Seal all open-
ings with tape.

3-7-3  Quick Connects, Flow Control  Valves  and other Connectors  - All connectors,
valves,  and other small parts should be packed in  small parts cabinets, trays  with
divided compartments,  or storage chests with labeled drawers  to provide quick and
easy access to the desired part.

3.7.4   Barometer - The field barometer should  be packed  in a rigid container,
securely mounted in rigid  foam.   The barometer  case should  be packed  in  a  larger
box designated to contain delicate or fragile equipment.

3.7-5  Thermometers and Thermocouple Readouts - Thermometers  and thermocouple read-
outs should be packed in the original carrying case,  if possible.   Glass thermome-
ters should be packed in  a rigid tube to prevent breakage.  These  items,  in their
smaller packing,  should also be packed  in a larger  box  designated  to contain deli-
cate or fragile equipment.

3«7-6  Method 4 Equipment -  Method 4 equipment should be packed following the  pro-
cedures recommended in Section 3.3.3 of this Handbook.

3.7.7  S-type Pitot Tube  and Differential Pressure Gauge - The S-type pitot tube,
when not mounted on the sampling probe, should packed  in a rigid  case and wrapped
with polyurethane foam,  polyethylene bubble-pack, or other suitable type of packing
material.  Seal all openings  with tape  or other, suitable material.   The differen-
tial pressure  gauge,  if not  part of a meter box,  should be  mounted in a rigid
o
o

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                                                                 Section No. 3.16.3
                                                                 Date June 30, 1988
                                                                 Page 33

 housing.  The gauge should be wrapped  with polyurethane foam, polyethylene bubble-
 pack,  or other suitable material, and packed in  a larger box designated for deli-
 cate and fragile  equipment.

 3-7-8  Glassware  - All  glassware  should be packed  in the original shipping contain-
 ers,  if available, and  stored together in  a larger rigid container marked "Fragile!
 Glass."  Otherwise, wrap the glassware with polyurethane foam, polyethylene bubble-
 pack,  or other suitable material, and pack in  a  rigid foam-lined container marked
 "Fragile! Glass."

 3.7.9   Tedlar Bags - Preferably,  transport the Tedlar bags to the field in individ-
 ual  rigid containers  used for  sampling.   If this is not  possible,  pack the bags,
 individually, in  corrugated  cardboard boxes with  the  connectors  secured such that
 they do not contact and puncture  the bags.

 3-7-10  Sampling Pumps  - Sampling pumps, if not mounted in a rigid housing suitable
 for transport, should be packed in a rigid foam-lined container.

 3.7.H   Dilution  Interface System - The dilution  interface  system  should be built
 into in a rigid container suitable for shipment.       •  :

 3-7-12   Gas Chromatograph System -  The  gas  chromatograph and  ancillary  systems
 should  be packed in the original  shipping  container for transport.   Although it is
 not recommended,  the GC can  be transported with out additional! packaging in a van
 or trailer provided the GC is secured properly against movement and other equipment
 is not  packed in a manner  where it  could fall on  the instrument.   For transport in
 dedicated  test  vehicles,  the  instruments should  be  mounted  in shock  absorbing
 devices.   All  gas lines and  analytical columns  should be capped to  prevent con-'
 tamination and/or oxidation during shipment.

 3-7-13  Gas Cylinders - All gas cylinders  should  be transported with their protec-
 tive cylinder heads securely attached.  The cylinders should be secured horizontal-
 ly so that they do not roll together or vertically in a specially designed cylinder
 rack.   Be aware of and  adhere to  all  Federal,  State,  and local regulations involv-
 ing the transport of compressed and flammable gases, particularly through tunnels.

 3.7.14  Liquid Organic  Compounds  - Liquid  organic compounds  should  be shipped with
 the container top sealed with electricians tape and stored in a sealed plastic bag.
Packed  each container in its original  shipping  box,  if available.   Otherwise, wrap
each container  individually  with polyurethane  foam,  polyethylene bubble-pack,  or
other suitable material and place in a box designated for chemicals.

 3.7.15  Dry Gas Meters - Dry gas meters not  housed in a  rigid meter  box suitable
 for transport should be wrapped with polyurethane foam,  polyethylene  bubble-pack,
or other suitable material, and packed in a larger box designated for delicate or
 fragile equipment.

-------
                                                                 Section  No.- 3-16.3
                                                                 Date  June  30,  1988
                                                                 Page  34


      Table 3.1.   ACTIVITY MATRIX FOR PRELIMINARY SURVEY SAMPLING AND ANALYSIS

Characteristic
Apparatus Check
Barometer
Wet bulb/dry bulb
thermometers
Method 4 equipment
S-type pitot tube
and differential
pressure
Probe
Teflon tubing
Quick connects
Glass flasks
High-vacuum pump
Tedlar or alumi-
nized Mylar bags

Acceptance limits
Within 2.5 mm
(0.1 in.) Hg of
mercury-in-glass
barometer
Within 1°C (2°F) of
a mercury-in-glass
thermometer
See Section 3.3.3
of this Handbook
See Section 3.1.3
of this Handbook
1. Clean; glass
liner, stainless
steel, or Teflon
inert to organics
2. Heating properly
if equipped with
heating system
3. Leak free
New and unused
New or clean
Clean
Vacuum of 75 n™
(3 in.) Hg absolute
Leak free; no
loss of pressure
after 30 seconds

Frequency and method
of measurement
Before each field trip
As above
Same as Section 3.3«3
Same as Section 3- 1-3
Before each field trip
following the proced-
ures described in Sub-
section 3«5-l
As above
As above
As above
As above
As above
As above
Prior to each test
pressurize to 5 to 10
cm (2 to 4 in.) H20

Action if
requirements
are not met
Repair or replace
Replace
Same as Section
3.3.3
Same as Section
3.1.3
Repeat cleaning
Repair or replace
As above
Obtain new tubing
Clean according
to manufacturer's
recommendation
Repeat cleaning
of flasks
Repair or replace
As above
                                                                                      o
                                                                                      o
(Continued)

-------
                                                                 Section No. 3-16.3
                                                                 Date June 30, 1988
                                                                 Page 35
Table 3.1  (Continued)

Charac teris tic
Apparatus Check
Rigid containers
Direct pump
sampling system
Needle valve and
rotameter
Adsorption Tube
Procedure
Adsorption tubes
Personnel sampling
pump
Extraction solvent
Teflon tubing
On-site Measure-
ments and Sampling
Wet bulb/dry bulb
measurement

Acceptance limits
Leak free; no
loss of pressure
after 30 seconds
Leak free; no
loss of pressure
after 30 seconds
Clean
Proper type of
adsorption material
Calibrated
Proper type of
extraction solvent
New and unused
1. Wet bulb wick
moistened
2. Wet bulb temper-
ature stabilized
3. Record wet bulb
and dry bulb
temperature

Frequency and method
of measurement
Prior to each test
pressurize to 5 to 10
cm (2 to 4 in.) H20
As above
Prior to each trip or
at the sign of erratic
behavior
Before each field trip
As above
Prior to extraction
of tubes for analysis
Before each field trip
Prior to each
measurement
During measurement
Immediately after wet
bulb temperature
stabilizes

Action if
requirements
are not met
Repair or replace
As above
Clean following
manufacturer1 s
recommendations
Replace with
proper type
Repair or replace
Replace with
proper type
Obtain new tubing
Moisten
Allow to
stabilize
Repeat
measurement
(Continued)

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                                                                 Section No. 3.16.3
                                                                 Date June 30, 1988
                                                                 Page 36
Table 3.1  (Continued)
                                                                   o
Characteristic
On-site Measure-
ments and Sampling
Evacuated glass
flask sampling
Purged glass
flask sampling
 Acceptance limits
1. Flask evacuated
to pump capacity

2. Assemble; no
leakage
                    3« System purged up
                    to flask inlet

                    4. Stopcocks closed
                    and taped; flask
                    labeled

                    5- Flue gas tempera-
                    ture and static
                    pressure determined
1. Assemble; no
leakage
                    3. Entire system
                    purged for 2 minutes
                    3. Stopcocks closed
                    and taped; flask
                    labeled

                    4. Flue gas tempera-
                    ture and static
                    pressure determined
Frequency and method
   of measurement
Prior to sample
collection

Before sample col-
lection, visually and
physically inspect
all connections

Immediately prior to
sampling

Immediately after
sampling
                      Immediately after
                      sampling
Before sample col-
lection, visually and
physically inspect
all connections

Immediately prior to
sampling
                      Immediately after
                      sampling
                      Immediately after
                      sampling
Action if
requirements
are not met
Evacuate flask
                                                                  Check for leaks;
                                                                  repair system;
                                                                  repeat test
Purge system up
to flask inlet

Close and tape
stopcock; label
flask

Determine flue
gas temperature
and static
pressure
                                             O
Check for leaks;
repair system;
repeat test
Purge entire
system for 2
minutes

Close and tape
stopcock; label
flask

Determine flue
gas temperature
and static
pressure
(Continued)
                                                                                       O

-------
                                                                 Section No. 3-16.3
                                                                 Date June 30, 1988
                                                                 Page 37
Table  3.1   (Continued)
Characteristic
On-site Measure-
ments and Sampling
Flexible bag sam-
pling procedure
Adsorption tube
sampling procedure
Preliminary Survey
Sample Analysis

Calibration
standards
(Continued)
  Acceptance limits
 1.  Assemble  using
 Figure  4.4;  no
 leakage
                    2. Flow rate set to
                    0.5 1pm; purge sy-
                    stem up to bag inlet

                    3. Flue gas tempera-
                    ture and static
                    pressure determined

                    4. Bag labeled and
                    protected from
                    sunlight
1. Assemble  using
Figure 4.9.  no
leakage
                    2. Tubes capped,
                    labeled and stored

                    3- Flue gas tempera-
                    ture and static
                    pressure determined
1. Minimum of three
standards prepared
for each analyte

2. Sufficient peak
resolution achieved
(valley height <25#
of the sum of the 2
peak heights)
Frequency and method
   of measurement
Before sample col-
lection, visually and
physically inspect
all connections

Immediately prior to
sampling
                       Immediately  after
                       sampling
                       Immediately  after
                       sampling
Before sample col-
lection, visually and
physically inspect
all connections

Immediately after to
sampling

Immediately after
sampling
Prior to sample
analysis
                                          During multiple
                                          component standard
                                          analysis
Action if
requirements
are not met
Check for leaks;
repair system;
repeat test
Set flow rate
Purge system up
to flask inlet

Determine flue gas
temperature and
static pressure

Label bag and
protect from
sunlight-
Check for leaks;
repair system;
repeat test
                                               Cap,  label  and
                                               store tubes

                                               Determine flue
                                               gas temperature
                                               and static  press.
Prepare three
standards for
each analyte

Vary GC operating
conditions and/or
change column
type

-------
Table  3.1   (Continued)
                                                                 Section No. 3.16.3
                                                                 Date June 30, 1988
                                                                 Page 38
                                                                o
Characteristic
 Acceptance limits
Frequency and method
   of measurement
Action if
requirements
are not met
Preliminary Survey
Sample Analysis

Calibration
standards
3. Response for
consecutive repli-
cate injections of
each standard agree
within 5% of their
average response

4. Calibration curve
generated
                    5. Audit sample
                    (optional) analysis
                    results within iO%
                    of true value
During calibration
standard analysis
Repeat injections
After calibration
standard analysis


As above
Perform regres-
sion analysis and
plot curve

Repeat audit;
remake and
reanalyze
standards
                                                                O
Glass flask sample
analysis
(Continued)
1. Condensation in
sample flask
                    2. Flask not
                    pressurized

                    3. Condensation in
                    pressurized flask
                    after 10 minute
                    equilibration
                    4. Adequate resolu-
                    tion between peaks
                    achieved for peaks
                    >5% of total area

                    5. Retention times
                    of consecutive in-
                    jections determined
                    and agree within 0.5
                    seconds or 1%
Before sample analysis
                      As above
                      As above
                      During sample analysis
                      After sample analysis
Heat flask to
flue gas or duct
temperature

Pressurize flask
                        Heat flask to
                        vaporize conden-
                        sate; if flask
                        already heated,
                        release pressure
                        and repressurize

                        Vary GC operating
                        conditions and/or
                        change column
                        type

                        Repeat analysis
                                                                O

-------
                                                                 Section No. 3-16.3
                                                                 Date June 30, 1988
                                                                 Page 39
Table  3.1   (Continued)
Characteristic
 Acceptance limits
Frequency and method
   of measurement
Action if
requirements
are not met
Preliminary Survey
Sample Analysis

Flexible bag
samples
1. Response for
consecutive repli-
cate injections of
each sample agree
within 5% of their
average response

2. Stability of bag
samples acceptable
(second analysis
conducted an equal
number of days cor-
responding to the
the time elapsed
between sample col-
lection and first
analysis within 10%)
During sample analysis
                                          After second analysis
Repeat analysis;
diagnose GC
problem
                        Consider one
                        of the alternate
                        sampling methods
Adsorption tube
samples
1. Samples desorbed
for period specified
in referenced method
                    2. Response for
                    consecutive repli-
                    cate injections of
                    each sample agree
                    within 5% of their
                    average response

                    3. Desorption effi-
                    ciency >50#
Before sample analysis
                      During sample analysis
                      After sample analysis
Check referenced
method; desorb
for specified
period

Repeat analysis;
diagnose GC
problem
                        Evaluate more
                        vigorous desorp-
                        tion techniques;
                        Consider one of
                        the alternative
                        sampling methods

-------
                                                                 Section  No.  3.16.3
                                                                 Date June 30,  1988
                                                                 Page 40
              Table 3.2.   ACTIVITY MATRIX FOR PRESAMPLINQ PREPARATION

Characteristic
Apparatus Check
Barometer
Wet bulb/dry bulb
thermometers
Method 4 equipment
S-type pitot tube
and differential
pressure
Probe
Teflon tubing
Quick connects
Sampling pump
Tedlar bags
Rigid containers

Acceptance limits
Within 2.5 mm
(0.1 in.) Hg of
mercury-in-glass
barometer
Within 1°C (2°F) of
a mercury-in-glass
thermometer
See Section 3.3.3
of this Handbook
See Section 3.1.3
of this Handbook
1. Clean; glass
liner, stainless
steel, or Teflon
inert to organics
2. Heating properly
if equipped with
heating system
3- Leak free
New and unused
New or clean
Leak free; adequate
delivery (>^ 1 Lpm)
Leak free; no
loss of pressure
after 10 minutes
Leak free; no
loss of pressure
after 30 seconds

Frequency and method
of measurement
Before each field trip
As above
Same as Section 3.3.3
Same as Section 3- 1.3
Prior to each trip
follow the cleaning
procedure described
in Subsection 3«5«1
Prior to each trip
As above
As above
As above
Prior to each trip
check with a rotameter
Prior to each test
pressurize to 5 to 10
cm (2 to 4 in.) H20
Prior to each test
pressurize to 5 to 10
cm (2 to 4 in.) H20

Action if
requirements
are not met
Repair or replace
Replace
Same as Section
3.3.3
Same as Section
3-1.3
Repeat cleaning
Repair or replace
As above
Obtain new tubing
Clean according
to manufacturer's
recommendation
Repair or replace
As above
As above
o
                                                                                      o
                                                                                      o
(Continued)

-------
                                                                 Section No. 3.16.3
                                                                 Date June 30, 1988
                                                                 Page 41
Table 3.2  (Continued)
Characteristic
 Acceptance limits
Frequency and method
   of measurement
Action if
requirements
are not met
Apparatus Check

Direct pump
sampling system
Leakfree; no
loss of pressure
after 30 seconds
Prior to each test
pressurize to 5 to 10
cm (2 to 4 in.)
As above
Needle valve and
rotameter
Clean
Prior to each trip or
at the sign of erratic
behavior
Clean following
manufacturer's
recommendations
Explosion risk
area sampling
system
Leakfree  (no vacuum
loss after 1 minute)
Prior to each trip
Repair or replace
Heated bag
sampling container
1. Leakfree; no
loss of pressure
after 30 seconds
                    2. Heating properly
Prior to each test
pressurize to 5 to 10
cm (2 to 4 in.) H20
                      As above
As above
                        As above
Direct interface
sampling system
1. Heating properly

2. Leakfree (no
flow at rotameter
with probe plugged)
As above

As above
As above

As above
Dilution interface
sampling system
1. Heating properly

2. Flowmeters cali-
brated
                    3.  Leakfree;  no
                    loss of pressure
                    after 30 seconds
As above

Calibrate prior to
each test against a
bubble meter or
spirometer

Prior to each test
pressurize to 5 to 10
cm (2 to 4 in.) H.,0
As above

Calibrate
Gas chromatograph
equipment
Leakfree, opera-
tional, and suffi-
cient spare parts
for the duration of
the field test
Prior to field test
check system for
leaks, access opera-
tional condition, and
inventory spare parts
Consult the
operator's
manual
(Continued)

-------
                                                                 Section No. 3.16.3
                                                                 Date June 30, 1988
                                                                 Page 42
                                                                                     o
Table  3.2   (Continued)
Characteristic
                     Acceptance limits
                      Frequency and method
                         of measurement
                        Action if
                        requirements
                        are not met
Reagents and
Equipment

Charcoal adsorber
                    Sufficient supply
                      Check supply prior to
                      each field test
                        Procure more
                        adsorbent
Adsorption tubes
                    Proper adsorbent,
                    tube size, and
                    quantity for test
                      Prior to field test
                      refer to Method
                      Highlights Section and
                      preliminary survey
                      results
                        Procure proper
                        adsorbent, tube
                        size, and
                        quantity
Gas chromatograph
carrier gas
                    Carrier gas compat-
                    ible to GC and
                    column; sufficient
                    quantity for test
                      Prior to field test
                      refer to operator's
                      manual or consult
                      with manufacturer
                        Procure compat-
                        ible carrier gas
                        in sufficient
                        quantity
                                                                                     O
Auxiliary GC gases
Proper type and
grade for GC detec-
tor; sufficient
quantity for test
Prior to field test
refer to operator's
manual or consult
with manufacturer
Procure proper
type and grade
of gases in suf-
ficient quantity
Calibration gases
                    Proper component(s)
                    and range; suffi-
                    cient quantity for
                    any on-site calibra-
                    tions
                      Prior to field test
                      refer to the prelim-
                      inary survey results
                        Obtain gases with
                        the proper compo-
                        nents in the
                        necessary range
                        and quantity
Calibration gas
dilution system
                    1. Rotameters clean
                    and calibrated
                    2. Dilution ratio
                    known (optional)
                      Prior to field test
                      examine and calibrate
                      following procedures
                      in Subsection 2.2

                      Prior to field test
                      establish the ratio
                      following the proced-
                      ures in Section 5-0
                        Clean and
                        calibrate
                                                                  Check dilution
                                                                  ratio prior to
                                                                  analysis
                                                                  (required)
Zero gas
                    Hydrocarbon-free
                    (<0.1 ppmv  as pro-
                    pane or carbon equi-
                    valent) ;  sufficient
                    supply for  test
                      Analyze or consult
                      manufacturer
                        Procure hydro-
                        carbon-free gas
                        in sufficient
                        quantity for test
                                                                                     O
(Continued)

-------
                                                                 Section No.  3.1613
                                                                 Date June  30,  1988
                                                                 Page 43
Table 3.2   (Continued)

Characteristic
Audit gases
Organic compounds
for preparing
gaseous standards
Equipment for
preparing gaseous
standards
Packing Equip-
ment for Shipment
Probe
Teflon tubing,
sampling lines,
and vacuum lines
Quick connects,
flow control
valves, and other
connectors
Barometer
Thermometers and
thermocouple read-
outs
Method 4 equipment
S-type pitot tube
and differential
pressure gauge

Acceptance limits
Required audit gases
in proper range
Target compound (s)
99 -9# pure or of
known purity
See Subsection
3.6.10
Protect with suit-
able packing
material
Coiled and taped;
openings taped
Stored organized
in containers
Packed in rigid foam
in a rigid container
Packed in original
container, if pos-
sible, or rigid
container
See Section 3.3-3 of
this Handbook
See Section 3-1.3 of
this Handbook

Frequency and method
of measurement
Prior to field test
contact EPA or vendor
(see Subsection 3.6.8)
Prior to field test
contact manufacturer
or vendor
See Subsection 3.6.10
Prior to each shipment
As above
As above
As above
As above
As above
As above

Action if
requirements
are not met
Acquire required
audit gas(es)
Procure 99.9#
pure compound(s)
or compound(s) of
known purity
See Subsection
3.6.10
Repack
Coil and tape
Repack
As above
As above
See Section 3-3.3
of this Handbook
See Section 3-1.3
of this Handbook
(Continued)

-------
                                                                 Section No.  3-16.3
                                                                 Date June 30,  1988
                                                                 Page 44
                                                                                    o
Table 3.2  (Continued)
Characteristic
                     Acceptance limits
                      Frequency and method
                         of measurement
                        Action if
                        requirements
                        are not met
Packaging Equip-
ment for Shipment

Glassware
                    Packed in original
                    shipping containers,
                    if available, or
                    suitable packing
                    material and marked
                    "Fragile"
                      Prior to each shipment
                        Repack
Tedlar bags
                    Packed in rigid sam-
                    pling containers, if
                    possible, or packed
                    individually in cor-
                    rugated boxes with
                    connectors secured
                      As above
                        As above
                                                                                    O
Sampling pumps
and dry gas meters
Mounted in a rigid
housing or packed in
rigid foam-lined
containers
As above
As above
Dilution interface
system
                    Built into a rigid
                    container suitable
                    for shipment
                      As above
                        Rebuild into
                        rigid container
                        or pack in suit-
                        able material
Gas chromatograph
system
                    Packed in original
                    shipping container,
                    secured properly in
                    van or trailer, or
                    mounted in a desig-
                    nated test vehicle
                      As above
                        Repack
Gas cylinders
                    Protective heads on,
                    secured in van or
                    trailer; transported
                    in compliance with
                    Federal, state, and
                    local regulations
                      As above
                        Repack; check
                        Federal, s tate,
                        and local regu-
                        lations concern-
                        ing transport of
                        compressed gases
Liquid organic
compounds
                    Top sealed and pack-
                    ed in original ship-
                    ping container
                       As above
                        Tape and repack
                                                                O

-------
                                                                Section No.  3.16.4
                                                                Date June 30,  1988
                                                                Page 1
4.0   ON-SITE MEASUREMENTS
    On-site  activities  include  transporting  the  equipment  to  the  test  site,
 unpacking and assembling the sampling and/or analytical equipment,  then conducting
 the sampling and/or analysis for the predetermined organic compound(s).   The qual-
 ity assurance activities for the on-site measurements  are summarized  in Table 4.1
 at the end  of this section.   Copies of  all field  data  forms mentioned  in  this
 section are  in Subsection 3.16.12.  The on-site measurements checklist. Figure 4.10
 at the end of this  section,  provides the  tester with  a quick  method  for checking
 requirements  during  sampling.

 4.1  Transportation  of Equipment to the Sampling Site

    The most  efficient  means  of  transporting the  equipment  from  ground  level to the
 sampling  site (often above ground level) should be  decided during  the preliminary
 survey or by prior correspondence.   Care should be  taken  to prevent damage to the
 equipment or  injury  to test personnel during the moving.  A clean "laboratory" type
 area  free of excessive dust  and organic  compounds  should be located and designated
 for preparing the sampling systems  and conducting  sample recovery and  analysis, if
 applicable.

 4.2  Preliminary Measurements and Setup

    Method 18  strongly  recommends  that  a  preliminary survey and/or  laboratory
 evaluation be conducted prior  to  sampling and  analysis.   Unless  adequate prior
 knowledge of  the  source  or information  is available,  the presurvey  procedures
 described in  Subsection  3-0  on  presampling  operations should be followed to select
 an acceptable sampling and analytical approach.
    The accuracy of the sampling system(s)  following handling and transportation to
 the sampling  site  is determined using a cylinder gas  audit.  The integrity of the
 system(s)  is  confirmed  after  setup  by conducting  the  individual system  check
 described below for  the  applicable  sampling method.   Preliminary measurements will
 always  include determining  the  stack dimensions  and the flue gas moisture.   Other
 measurements  which may be made depending upon the requirements of  the  applicable
 regulations and the  source operations include a flow  rate determination,  velocity
 check, and stack gas temperature range measurement.
    One  of the primary concerns for any organic sampling  program must  be  safety.
 The tester should always question  the facility representative  concerning  general
 plant  safety  requirements  and safety  in  regard  to  sampling at  the  selected
 sampling  site.    Every sampling and  analysis protocol  should  address  the  safety
 considerations involved  in  performing the  protocol.  Because  there are  numerous
 safety  considerations involved  in organic sampling,  it is  beyond the scope  of this
 Handbook  to discuss each one in detail.  However, it cannot be over-emphasiged that
 the tester must always be aware of the safety hazards.

 4.3 Sampling

    The  following  subsections discuss  the  procedures  for  each  Method  18  sampling
 technique.   At this point, the  tester has  selected the proper  sampling technique
 and checked  the selected sampling system.   If this has not been accomplished,  the
 user should refer to Subsection 3-0  prior to conducting the field test.

-------
                                                                Section No. 3-16.1*
                                                                Date June 30, 1988
                                                                Page 2

   Because  of the  complexity in  sampling organic compounds  from the  variety of
potential source  types,  only the more common problems are  addressed  for each sam-
pling  method.   Recommended  quality  assurance/control checks  and procedures  are
provided to assess  the suitability of the sampling technique for the samples to be
collected.  Because of  the relative compactness of the equipment  and the low cost
of many of the sampling techniques, the tester may be able to utilize two different
sampling techniques at  the same  time with little additional effort.   The samples
from the backup or secondary  technique  are not analyzed if  the primary technique
proves satisfactory.  For example, the tester might easily  run  an adsorption tube
system as  a  backup to  an  evacuated  bag  system.   At some  facilities, it  may be
necessary to  conduct two techniques  simply to  accurately measure  all  the organic
compounds of  interest.  The tester should always  be aware that a change in process
operations such as  raw materials, moisture content, operation mode, and temperature
can render a previously acceptable sampling technique unacceptable.
   The specific sampling system descriptions are provided below.

4.3.1   Evacuated Container Sampling  (Heated  and Unheated)  -  In  this procedure,
sample bags are filled by evacuating the rigid air-tight containers that hold them.
The suitability of  the  bags for sampling  should have  been  confirmed  by permeation
and retention checks using the  specific  organic  compounds of interest during the
presurvey operations.   The  means  of transporting  the bags to  the  laboratory  for
analysis within  the specified  time should also have  been determined.   Delays in
shipping and/or  analysis can  result  in  significant  changes in  concentration  for
many compounds.
   On-site sampling includes the following steps:
     1. Conducting  preliminary measurements and setup.
     2. Preparation and setup of sampling system.
     3. Preparation of the probe.                                        ;
     4. Connection  of electrical service and leak check of sampling system.
     5. Insertion of probe into duct and sealing of port.
     6. Purging of  sampling system.
     7. Proportional sampling.
     8. Recording data.
     9. Recovering  sample and transportion to laboratory.

   Preliminary Measurements and  Setup -  The  sampling site  should be  checked to
ensure that  adequate electrical  service  is available.   The stack dimensions  are
measured and recorded on a data sheet similar to the ones shown in Figures 4.1,  4.2
and 4.3.   The moisture  content of the  flue gas  is  used to correct  the measured
concentrations to a dry basis.   It is typically measured prior to sampling using
wet bulb/dry  bulb thermometers  or Method  4 (see Subsection 3^2); the determination
should be performed at a  time when process operations  are like they will be during
final sampling.   If the process  utilizes and  emits ambient  air,  a sling psychro-
meter may be used to measure the moisture content of the ambient air in the area of
process air uptake.  The moisture  content value  is also used to  confirm  that  the
sampling approach selected is acceptable.
   Prior to final sampling,  the tester must determine if the  final results are to
be presented  on a concentration basis or  a  mass  emission basis.  If  they will be
presented only on a concentration basis,  only the  concentrations  of  the specified
organics and the stack gas moisture content must be measured.  If the mass emission
rate of any  compound is  to  be presented, the flow rate  of the stack  gas  using a
velocity traverse must also be  determined.   In  this case,  although not required by
Method 18,  it is preferable that the sampling location be  selected in  accordance
/f-^.
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Plant KubUr C-rU>n L*- Flowmeter calib.(Y) O. ?1 <> Dilution
City 7y^s/7tf., /VC-
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Container volume, 3<2
Container number
Average (aP) &.
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Figure 4.1.  Field  sampling data fora for  container sampling.
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                                                                                             vD
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Plant l\ubk-&f^ Cb\JL*f^_ Co-
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Sampling point local
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initial Cotisfant/
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source flowrate 0.152. L/nin (cfn) Carrier gas flow
Meter box number /V/4
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                        Figure 4.2.  Field  sampling data form for  direct interface sampling.
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Plant 	
City
Operator
Date    /
                 Cklsn   Co.    Flowmeter  calib. (Y)   //2
Run number	
Stack dia, mm  (in.)    (D //}.
                                Adsorption tube type:
                                 charcoal  tube      X
                                 silica gel
                                 other
                                      Dilution system: (dynamic)
                                       emission flowsetting     /V/4
                                       diluent flowsetting
Meter box number
Pitot tube  (Cp)
Static press   ()
Adsorption tube number 	
Average (aP)     Q.4-  na  (in.)  H20
Initial flowmeter setting    A/2.
Average stack temp   ~7O
                   mm (in.)  1^0  Barometric press  .2-9.65" ma  (in.) Hg
Dilution system:  (static)
 emission flowsetting 	    	
Final leak check   0  m3/iain (cfin)
Vacuum during leak check     /O
	ma  (in.)  H.,0
Sampling point location	'
Sampling
time,
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Sim-fin.) H20,
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Flowmeter
setting
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Temperature r
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                                                                                                             tl O W
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                                                                                                             W ft O
                                                                                                             (0 (D ft
                    Figure 4.3.   Field sampling data form for adsorption  tube  sampling.
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                                                                                                               oo.
                                                                                                               OO.P-

-------
                                                                Section No. 3.16.4
                                                                Date June 30, 1988  x—^
                                                                Page 6              f  J

with  Method 1.  If this  is  impractical,  it  should be  selected to  minimize flow
disturbances. The number and locations of sampling points for the velocity traverse
are selected according  to Method  1  (see  Section 3.0.1  of this Handbook); the trav-
erse  is conducted  according to  Method  2  (see  Section 3-1 of this Handbook).  Note:
The Method 18 sampling will be conducted at a single point.
   Method  18  requires that samples  be collected proportionally, meaning  that the
sampling rate must be kept proportional to the  stack  gas  velocity  at the sampling
point  during  the sampling period.   If the process  has  a steady state  flow (con-
stant) , then the flow rate does not  have to be varied during sampling.  The major-
ity of sources of organic emissions are of this type because they use constant rate
fans. If the tester can confirm from the facility that the source of interest has a
steady state flow  (e.g., it uses a constant rate fan), then sampling can be conduc-
ted  at a constant  rate  and  no concurrent  velocity  measurements need to  be made.
If  it is not  known whether  the  process is  steady  state or  if it is  not steady
state, then velocity  measurements  (the velocity head)  must be made  at the point to
be  sampled.    This  can be  done during  the  preliminary  survey or before  final
sampling,  but  should be  done when  the  process operations  are  like they  will  be
during the final sampling.  The average  velocity head  (pitot reading)  and range of
fluctuation  is  determined and  then  utilized  to  establish  the  proper flow rate
settings during  sampling.   If  it  is found that  the process is not  steady state,
then  the  velocity  head must  be monitored  during  sampling to maintain  a  constant
proportion between the sample flow rate and the flow rate in the duct.
   Select a  total  sampling time greater than or equal to the minimum total samp-
ling  time  specified in the  applicable emission standard.   The number  of minutes
between readings while sampling should be an integer.  It is desirable for the time
between readings to be such that the flow rate does not change more  than 20% during
this period.
   If  it was  determined from the  literature  or the preliminary  survey  laboratory
work that the sampling system must be heated during sample collection and analysis,
the average stack  temperature is used  as  the  reference temperature  for the initial
heating of the system and should be determined.  Then,  the stack temperature at the
sampling point  is  measured  and  recorded during  sampling  to  adjust the  heating
system just above  the stack temperature or  the dew point.   In addition,  the use of
a heated sampling  system  typically requires that the analysis be conducted on-site
since it is not  practical to  maintain the sample bag  at  elevated temperatures for
long periods of time.

   Sampling  System Preparation  - Prepare  the  probe  and  sampling  train in  the
laboratory area  (see  Figure  4.4).    First,  place a loosely packed  filter  of glass
wool  in the  end  of the probe.  Attach a sample bag that has  been  previously leak
checked to the sample container lid.  Seal the inlet  to the probe  and  the sample
container  lid  to  the container body.    Transport the container  and probe  to  the
sampling site.

   Proportional  Sampling -  Sampling  must be conducted  at  a  rate  in  constant
proportion to the  stack gas  flow at the  sampling point. Thus, for  a  steady state
operation,  the sampling  flow  rate is not  varied during the run. For  a  non-steady
state  process,  the sampling  flow rate  is varied  in proportion  to  the  changing
velocity.   The velocity is monitored by measuring the velocity head  (AP)  which  is
linearly related to  the  square  of the velocity.   A recommended method  for deter-
mining proportional sampling  rates is as  follows:
   1. Conduct a single point velocity  check as previously  specified,  and determine
      the average velocity head  (APa   ) to be  sampled.
o

-------
                                                                          VENT
           STACK
           WALL
   FILTER

(GLASS WOOL)
D
  TEFLON
SAMPLE LINE
         f
  REVERSE
   (3") TYPE
 PITOT TUBE
                 PROBE
                                      VACUUM LINE
           MALE QUICK
           PONNECTORS.
NEEDLE
   VE
                BALL
           •f   CHECK
                  FLOWMETER!
                                            PUMP
                                                    CHARCOAL
                                                      TUBE
              PITOT MANOMETER
                       NO CHECK
                           RIGID LEAKPROOF CONTAINER
                  Figure 4.4. Integrated bag sampling system.
                                                                                  T3 O W
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                                                                                  OT rt O
                                                                                  (D (0 rt
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                                                                                    00'
                                                                                    CD 4=-

-------
                                                             Section No.  3.16.4
                                                             Date June  30,  1988
                                                             Page 8

2. The average sampling flow rate for the test is determined prior to  the  start
   of the  run.   Typically,  the  average sampling flow  rate  is about  0.5  L/min
   which will yield approximately 30 liters of sample.  The  flow rate  chosen  in
   the laboratory  should  fill the  bag  to about three  fourths of its  capacity
   during the sample run.   The average  flow rate chosen is then assigned to the
   average velocity head measured.
3. The flow rate to be  used  during sampling when the velocity head varies from
   the average is calculated  using the following equation.

                                                                   Equation 4-1
                  Q.  =
                                                                                 o
 where

      Q^ = Average sampling rate, L/min (ft3/min),
      Qg = Calculated sampling rate, L/min (ft3/min),
      AP = Actual velocity head, mm (in.)  H20,  and
   APavg = Average velocity head, mm (in.) H20.

   4. Determine  the  rotameter setting  for  the sampling  rate  (Qs)  from  the  rota-
      meter calibration curve, and adjust the rotameter accordingly.
Using this  procedure will  provide for the  correct sampling  rate  and  the  proper
filling of  the sample  bag.   Follow  the  procedure below to obtain  an  integrated
sample.
   1. If  a  heating  system is  required,  turn  on the  heating system  and set  at
      average stack temperature determined from the pretest measurements.
   2. Leak  check the sampling  train  just  prior  to  sampling by  connecting  a  U-
      tube,   inclined manometer,  or equivalent at  the probe  inlet and  pulling a
      vacuum of  >^ 10 in.  H20.  Close the needle valve and  then turn  the pump off.
      The vacuum should  remain stable for  at least  30  seconds.    If  a leak  is
      found, repair  before proceeding; if  not, slowly  release  the  vacuum  gauge.
      This leak check is optional.
   3- If  the system  is  being heated,  wait  for  it  to come  to  the  proper  tempe-
      rature.  Place  the  probe  in the  stack  at the sampling point:  centroid of the
      stack  or  no closer  to  the walls than  1 meter.    Seal the sampling port  to
      prevent dilution of the stack gas by inleakage of ambient air.
   4. Disconnect the flexible bag.  Purge  the system by turning on the pump and
      drawing at  least  5  times  the sampling  system volume through  the  train,  or
      purge for 10 minutes, whichever is greater.
   5. Adjust the  flow rate to  the proper setting  based on the  velocity pressure
      (during the purging, for non-steady state processes).
   6. Connect  the flexible   bag  to the  sampling  train  (the connections  should
      ensure a leakfree system),  and begin sampling.   The rate must remain propor-
      tional to the stack gas velocity for the total sampling time specified by the
      standard of performance for the industry being sampled.
   7. Record all  data required  (5  minute intervals,  miniumum) on  the  field  samp-
      ling  data  form (see  Figure 4.1).  The  flow rate  and sample  train  heating
      system should  be  adjusted after every pitot  and temperature reading to the   —
      correct level.                                                                  f  ^
   8. Disconnect and  seal the flexible bag upon completion  of  sampling.   Take care  \	J
      not to dilute the contents with ambient air.
   9- Label  each  bag clearly and uniquely  to  identify  it with its  corresponding
      data form and/or run.   If  the system is  a heated system, the  sample bag must

-------
                                                                Section No. 3.16.4
                                                                Date June 30, 1988
                                                                Page 9

      be maintained at the stack temperature through sample analysis.

   Sample  Recovery  and  Transport  to  Laboratory  -   Sample  recovery  should  be
performed  so as  to  prevent contamination  of the bag  sample and  maintain sample
integrity.   The bag should remain leakfree,  protected  from direct sunlight, main-
tained  at  a temperature that  will prevent condensation  of any of  the  gases,  and
stored  in  a safe place to  prevent damage or  tampering prior to analysis.   It is
recommended  that bag samples  be  analyzed within  two  hours of  sample collection,
however, many of the organic compounds  are  stable  enough to allow a few days prior
to  analysis.    Upon  completion of the  testing and  sample  recovery,  all  the data
forms should be checked for completeness  and  the sample bags reexamined for proper
identification.

   Common  Problems  -  The  most  common  problems  encountered with bag  sampling
techniques are  (1) adsorption  of the gases  on the  bag,  (2)  permeation of the gases
through the bag,  (3) reaction of gases in the bag,  (4)  condensation of the gases or
water vapor in  the bag, and  (5) leaks developing in  the bag during testing, trans-
port, and/or analysis.   As described previously in Subsection 3«0, the bags must be
checked for stability and retention of  the  compound  in  the  bag.   If the compound's
concentration significantly diminishes between the time the sample run is completed
and the time of analysis,  then the bag technique will have to be modified or rejec-
ted.  One  modification  that  can be used  to reduce both retention and/or condensa-
tion is addition of  a  heating system.   Heating is generally applied during sample
collection  and maintained  through analysis.    However,  heating  may  increase  the
permeation rate.   Another option  is  the  use of heat  lamps applied  to  the sample
bags after sample collection  and during sample  analysis.   Two other  techniques
that have been  used to prevent condensation are  (1)  addition of a knockout trap to
remove  water vapor  and heavy  organics  from  the  sample  stream, and (2)  use  of
sorbents such as Tenax to remove the high boiling  point organics.  The tester must
demonstrate  that  the  organic  coiapound(s)  of  interest  are  not   removed.
Alternatively,  sample and/or water vapor  condensation may be reduced by the use of
the prefilled«  bag technique.   The prefilling of  the bag lowers  the concentration
of the organic and/or water vapor,  thereby eliminating condensation.
   If the gases  are reacting in the bag,  then the  bag  material can be changed,  the
time between sample collection and analysis reduced, or a different technique used
such as direct  interface  sampling. Methods to reduce bag leak problems  are proper
construction of  the sample bags, conducting additional  runs,  using a backup sample
collection technique such as  an another bag sampling system or  an  adsorption tube
sampling system,  and care with handling the sampling bags.   Also,  steel canisters
can be  used  in  place of the bags.   If  the organic compounds  are  stable with time,
the use of steel canisters may better ensure the safety of the sample especially if
the samples must be air freighted to the laboratory for analysis.

4.3'2 Direct Pump Sampling - Direct pump  sampling  is conducted in a manner similar
to evacuated container  sampling, with  the exception that the  needle valve and  the
pump are located between  the  probe and sample bag and  the  sample exposed surfaces
of both must be constructed of stainless steel, Teflon  or other material not affec-
ted by  the stack  gas  (see Figure 4.5).    Due to  the  additional likelihood that
sample may be lost in the needle valve  and pump, it  is  recommended that the probe,
sample line,  needle valve,  and pump be heated.  If  it has or can be shown that this
not a concern,  then the heating may be eliminated.   All precautions,  procedures,
data forms and  criteria from Subsection  4.3-1 above can be applied.   Ensure that
the system has  been adequately purged  before attaching  the bag and sampling.

-------
                                                Stainless
                                              Needle Vafvo
    Filter
 (Glass Woo!)
 Reverse
 (3") Type
Pitot Tube
                                                                                       Rotamotar
                                                                 Teflon-Lined
                                                                  Diaphragm
                                                                    Pump
 O
                                                                                      Protective Container
                                       Figure 4.5-   Direct  pump sampling system.
o
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                                                                                                                           Lino
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-------
                                                                Section No. 3.16.4
                                                                Date June 30, 1988
                                                                Page 11
 4.3-3   Explosion  Risk Area Bag Sampling - Explosion risk area bag sampling is also
 similar to  evacuated container sampling.   The major difference is that no electri-
 cal  components  can  be used in the explosion risk area.   As previously mentioned in
 Subsection  1.0, the first option of the  tester  is  to  locate the electrical equip-
 ment (e.g.,  the pump)  outside the explosion risk area and run a long flexible line
 to the  container.   If  that option is not possible, an evacuated steel container may
 be used as  shown  in Figure 4.6.  This  option may involve a potential spark hazard
 and  must be checked though the plant safety officer.   No electrical heating of the
 system  will likely  be allowed.  If  an  evacuated steel  container is used, the leak
 check can be conducted outside the  explosion risk area and the probe can be purged
 with a  hand squeeze pump.  The  tester may wish to consider an alternative method of
 sampling such as  adsorption tubes and an" intrinsically safe personnel sampling pump
 or the  syringe method. The primary concern must be safety in an explosion risk area
 and  all operations  must be outlined  in writing and cleared through the Plant Safety
 Officer.   The  same criteria as  described above for  suitability of the  bag will
 apply and must be met.

 4.3.4   Prefilled  Bag Sampling - The prefilled bag sampling technique is similar to
 the  heated  direct pump sampling method.   The major difference  is  that the sample
 bag  is prefilled with  a known volume of nitrogen, hydrocarbon-free air, or cleaned,
 dried ambient  air prior  to  sampling and the  volume  of gas sampled  must be accu-
 rately  determined (see Figure 4.5).   When using  a  flowmeter or metering pump, the
 maximum dilution that  should be attempted is 10 to 1.  Alternatively, a heated, gas
 tight syringe may be used to collect the gas at  the source  and inject  it into the
 sample bag.  A  heated, gas tight syringe can be used for dilutions  of  5 to 1 when
 the  dilution is performed in  the  syringe and 50  to  1 when performed  in the bag.
The use of  a heated,  gas  tight syringe  should follow the procedures shown below in
Subsection  4.3«5.    Both techniques  should  be  verified•„in the laboratory using
higher concentrations of calibration gases and must be within 10% of the calculated
value.   The technique  is  verified in the field by diluting  the audit gases in the
same manner as the stack gases  (see Subsection 8.0 for auditing procedures).
   Following are the recommended steps to conduct prefilled bag sampling:
   1.  The sampling  should  be conducted proportionally as described  above in Sub-
       section 4.3.1.  Calculation of the  average sampling  rate vs.  the average  P
       will be the  same with the exception that the volume  of the  prefilled inert
       gas must be taken into account.
   2.  The  suitability of the  prefilled bag sampling  technique should  have  been
       checked  in the  laboratory.   This  would  include  calculating the  dilution
       factor required to obtain ;an acceptable sample concentration.
  ' 3«  In the laboratory  area,  fill the sample bag  (previously leak checked)  with
       the  calculated  volume of inert  gas.   Because  of  the potential  for leaks,
       bags  should  be filled  the  same  day  they are used.   The inert  gas volume
       must be determined with  a calibrated dry gas meter or  mass  flowmeter.   The
       bag should  be sealed and taken to the sampling site.
   4.  At the sampling site, the sampling system is leak checked without the
       sampling bag  attached.   Turn on  the  heating system and heat  the  system to
       the stack temperature.   Connect  a U-tube  H20 manometer  or equivalent to the
       inlet of the  probe.  After the system comes to the desired temperature,  turn
       on the pump  and pull a vacuum of about 10 in. of H20.   Turn  off the needle
       valve and  shut off  the pump.   If there  is no noticeable  leak within  30
       seconds,  then the system is leak  free.
   5.  Place the probe in the stack at the sampling point  (centroid  or no less
                                          /i.

-------
                                                             PVC Tubing-
                                                                                       Directional
                                                                                         Nead!o
                                                                                         Vafvo
                                                                                                      Quick Disconnectors
  Probo
 5'Triton
  Tubing
o
                     Figure ^.6.   Explosion  risk area  sampling system option using an
                                    evacuated  steel container.
                                                                                                                co -c-
o

-------
   6.
   7-


   8.

   9.
                                                         Section No. 3.16.4
                                                         Date June 30, 1988
                                                         Page 13

than 1 meter from the wall)  and  seal  the  port so there will be no inleakage
of  ambient  air.   Turn on  the pump  and  purge  the  system for  10  minutes.
During the  time that the  system is  purging,  determine and set  the proper
flow rate based on the Ap.
Turn off the pump and attach the sample bag.  Compare the heating system
The sampling will  be conducted  proportionally.   The  stack temperature and
heating system  temperature should  be monitored and  recorded.    Record 'the
data on the sampling data form (Figure 4.1).
At  the conclusion  of the run, turn off  the pump and  remove the probe from
the duct.   Remove the bag and seal it.
Conduct a final leak check.   The  system  should pass  the  leak  check;  if  it
does not pass,  repeat the run.
4.3-5  Heated Syringe Sampling - The  heated  syringe  technique can be used with the
prior approval of the Administrator.  This technique should only be used when other
techniques are impractical.  The heated syringe technique requires on-site analysis
with three syringes collected and analyzed for each  run.   The requirements for the
use of the syringes are the  same as for the  bag  with regard to the reaction of the
gases with time and the retention of the gases in the syringe.
   Following are the procedures recommended for the syringe sampling technique:
   1.  If heating  is  required,  then  the  syringe must be encased  in material that
       has a  high  density to maintain  the  proper temperature.   Alternatively,  an
       external heating  system can be  used  that keeps  the syringe at  the proper
       temperature until  just  before use and  to which the syringe  can  be immedi-
       ately returned.
   2.  The access  port  should be extremely  small to prevent  inleakage  of ambient
       air.   The port  may be covered  with Teflon  or other  nonreactive material
       that will allow the syringe to penetrate the material for sampling.
   3.  For the  direct  injection  method  (no dilution), place the  syringe needle
       into the stack and fill  and discharge the full volume  that will  be sampled
       three times.   Then,  draw  the emission sample  into  the syringe,  immediately
       seal the  syringe  and return  to the heating system,  if  applicable.   The
       second and  third syringes  are sampled at equal  time intervals  spanning the
       required sample  (run)  time.   The syringe samples  must  not be  taken one
       immediately after another.
   4.  For  the  diluted  syringe  method, the  inert  gas  is  introduced into  the
       syringe three  times  and discharged.   Following this,  the  proper volume  of
       inert gas is pulled  into  the syringe.  The syringe  is  then placed into the
       duct and the proper volume of stack  gas  is  added.    Immediately  remove the
       syringe needle from  the duct,  seal the syringe,  and return  to the heating
       system, if applicable.
   5.  For the bag diluted syringe method,  the  bag  should be prefilled  with the
       proper volume  of  inert  gas.    The  sampling is conducted as  described above
       and the sample injected into the bag through  a septum.
   6.  Record the data on a field sampling data form (can adapt Figure 4.1).
   7.  Since   the  method  requires  a  proportional   sample   to be  collected,  the
       velocity head  (AP) should  be recorded at about  the  same  time   that  each
       sample  is  collected.    The  concentrations  can  then  be  mathematically
       corrected  to provide an integrated  value.   If the  process  is  a  constant
       source  operation (less  than  10% change in flow over the  sampling period),
       it is not  necessary to correct  the measured values.

-------
                                                                Section No. 3.16.4
                                                                Date June 30, 1988
                                                                Page 14

4.3.6   Direct  Interface Sampling  - The  direct interface  procedure can  be used
provided  that the moisture  content  of the  stack  gas does not  interfere with the
analysis  procedure,  the physical requirements  of  the equipment can be  met at the
site,  and the source gas concentration  is low enough  that  detector saturation is
not a  problem.   Adhere  to all safety requirements  when using this method.  Because
of the amount of time the GC takes  to resolve the organic compounds prior to their
analysis,  the GC  can only  typically make  three  analyses  in a  one-hour period.
Therefore,  the number of injections  in the direct  interface method is greatly lim-
ited  by   the  resolution time.   At  least  three injections  must be  conducted per
sample run.
   Following  are  the procedures  recommended  for  extracting a  sample  from  the
stack, transporting  the  sample through a heated sample line,  and introducing it to
the heated sample loop  and  the GC.   The analysis  of the sample  is  described in
Subsection  5-0.
   1.  Assemble  the  system as  shown Figure 4.7, making all connections tight.
   2.  Turn on the sampling  system heaters.   Set the heaters to maintain the stack
       temperature as indicated by  the stack thermocouple.   If this temperature is
       above  the safe operating temperature of the Teflon  components,  adjust the
       heating system to maintain a temperature adequate to prevent condensation of
       water  and organic compounds.
   3.  Turn on  the  sampling pumps  and  set  the flow  rate at  the  proper setting.
       Typically 1 L/min is  used.
   4.  After  the system reaches the same temperature  as  the stack,  connect a U-
       tube H20  manometer  or  eqivalent  to the inlet of the probe.   Pull a vacuum
       of about  10 in.   of H20, and shut off  the  needle valve  and then the pump.
       The  vacuum should  remain stable for  30 seconds.   If the  system leaks,
       repair and then recheck the system.
   5.  Calibrate  the  system  as  described  in  Subsection  5-0.    Repeat  until
       duplicate analyses are  within 5% of their mean value (Subsection 5«0).
   6.  Conduct  the analyses  of the  two audit  samples as described  in Subsection
       8.1.   The results must  agree  within  10% of the true value  (or greater, if
       specified on  the  cylinder).   If the results  do not agree, repair the system
       and  repeat the analyses until agreement is met or until approval is given by
       the  representative of the Administrator.
   7.  After  the audit  has  been successfully  completed,  place  the inlet  of  the
       probe  at  the  centroid  of the duct,  or  at  a point  no  closer  to  the walls
       than 1 meter, and draw stack gas into  the  probe,  heated line,  and sample
       loop.  Purge the system for a least 10 minutes.
   8.  Record the field sampling data on a form such as Figure 4.2.
   9.  Conduct the analysis  of the  sample  as described in Subsection  5«0.   Record
       the  data  on the  applicable  data form (Figure 5-1, Subsection  5.0).   Ensure
       that the  probe  and  sample  lines  are maintained  at 0°C  to 3°C  above  the
       stack  temperature (or a temperature which prevents condensation).
   10. Conduct the posttest calibration as  described in Subsection 5.0.

4.3.7  Dilution  Interface Sampling -  Source  samples  that  contain a high concentra-
tion  of   organic materials  may require dilution  prior  to  analysis  to  prevent
saturating  the  GC detector.   The  apparatus  required for  this direct  interface
procedure is  basically  the  same as  described above,  except  a dilution  system is
added between the heated sample line  and the gas sampling  valve.   The apparatus is
arranged so that either a 10:1 or 100:1  dilution of  the source gas  can be directed
to the chromatograph.  The description of the  apparatus  is  presented in Subsection
/"""N
f   )
^—'
o

-------
                                                                   MANOMETER
                                  TC      TC READOUT
                               READOUT OR CONTROLLER
GLASS
WOOL
 1/2-in.
TUBING

                  1/4-in. SS
                  TUBING
         STACK WALL


                   f—"*•»  "~^ "VS"*™**.,.
                   mmm
               	-™V - >-ji___j—?
                                        INSULATION
                           EMPERATUR
                           CONTROLLER
                                                                       °| NEEDLE
                                                                           VALVE
                                                        HEATED
                                                       [EFLON LINE
                                                            HEATED GAS
                                                          SAMPLING VALVE
                                                               SNGC
                                             AUDIT
                                            SAMPLE
                                               EM
                                                                                CHARCOAL
                                                                                ADSORBER
                   FLOWMETER
 PUMP
TO GC INSTRUMENT
                                                                        CARRIER IN
                                  Figure k.J.  Direct interface sampling system.
                                                                                                  TJ a en
                                                                                                  o p a>
                                                                                                  (ft ft O
                                                                                                  n> a> 
-------
                                                                Section No.  3-16.4
                                                                Date June 30,  1988
                                                                Page 16

1.1.9  and the  pretest calibration  of the  apparatus is  presented in  Subsection
2.2.1.
   Following  are  the procedures  recommended  for  extracting  a sample from  the
stack,  diluting the  gas  to the  proper level, transporting  the sample  through a
heated  sample line,  and  introducing it to the heated sample loop and  the GC.   The
analysis of the sample is described in Subsection 5.0.
   1.  Assemble  the  apparatus  by connecting  the heated box,  as  shown  in  Figure
       4.8, between  the heated sample line  from  the probe  and the  gas sampling
       valve  on the  ehromatograph.  .  Vent the source  gas from the  gas sampling
       valve directly to the charcoal filter,  eliminating the pump and rotameter.
   2.  Measure  the stack temperature,  and adjust  all heating  units  to  a  temper-
       ature 0°C to 3°C above this temperature.  If the temperature is above the
       safe operating  temperature of the  Teflon components, adjust  the  heating to
       maintain  a  temperature  high enough to prevent  condensation of  water  and
       organic compounds.
   3.  After the heaters have come to  the proper temperature,  connect a U-tube H20
       manometer or eqivalent to the inlet of the probe.   Turn on the pump and pull
       a vacuum  of about 10 in.  of  H20.   Shut off the  needle  valve and then turn
       off the pump.  The vacuum reading should remain stable for 30 seconds.  If a
       leak is present, repair  and then recheck the system.
   4.  Verify operation of  the  dilution system by  introducing a calibration gas at
       the inlet of the probe.  The diluted calibration gas should be within 10% of
       the calculated  value.    If  the  results for  the diluted  calibration  gas are
       not within  10%  of the expected values, determine whether the GC and/or the
       dilution  system is  in  error.   If the  analyses  are not within  acceptable
       limits because of  the  dilution system,  correct  it  to  provide  the proper
       dilution  factors.    Make this correction by  diluting a  high concentration
       standard gas mixture to  adjust the dilution ratio as required.
   5.  Verify the  GC  operation  using a low concentration standard by diverting the
       gas into  the  sample loop and bypassing the dilution system  as described in
       Subsection 5-l«  If  these analyses are not within acceptable limits, correct
       the GC by recalibration, etc.
   6.  Conduct  the analyses of the two  audit  samples  as described in  Subsection
       8.1 using either  the dilution  system  or directly  connect  the gas sampling
       valve as  required.   The results must  agree within  10#  of the true value or
       greater value  if  specified on  the  cylinder.   If the  results do not agree,
       repair the  system and repeat the  analyses  until  agreement is  met or until
       approval is given by the representative of the Administrator.
   7.  After the dilution  system  and  GC  operations  are properly verified  and the
       audit successfully  completed,  place the probe at the centroid of the duct
       or at a  point no  closer to  the walls  than  1  meter, and  purge the sampling
       system for at least  10 minutes  at  the  proper  flow rate.   Conduct the analy-
       sis of  the  sample  as  described in Subsection 5.0.   Record the  field and
       analytical data on the applicable  data forms  (Figures  4.2 and 5-l)«   Ensure
       that the probe, dilution system, and sample lines are  maintained at 0°C to
       3°C above  the stack  temperature (or  a temperature which prevents  conden-
       sation) .
   8.  Conduct the posttest calibration and verification of  the dilution system as
       described in Subsection 5.0.
   If the  dilution system is used  for bag sampling,  the  procedures  for verifying
operation of  the dilution  system will be the same  as  shown  above.  The  diluted
calibration gas  will be  collected in  a  bag  and  then verified.   Also  the  audit
samples will be collected in a bag and analyzed.  Acceptable results must be
o
o

-------
                                            Vent to Charcoal Adsorbers
Heated Line
from Probe
                Quick
               Connect
                                                            Quick
                                                          Connects to
                                                          Gas Sample
                                                            Valve
                             Source
                           Gas Pump
                            1.5L/Min
                   150 cc/Min
                     Pump
150 cc/Min
  Pump
                                                    3-Way
                                                    Valves
                                                    in 100:1
                                                    Position
 Check Valve
Quick Connects
 for Calibration
Flowmeters
(On Outside
  of Box)

Flow Rate of
1350 cc/Min
                                          Heated Box at 120° C or Source Temperature
                                                          U
                                                                                                                       •ti o (/>
                                                                                                                       P  p 0>
                                                                                                                       m  rt o
                                                                                                                       (0  (0 rt
                              To Heated GC Sampling Valve
                                                                                                                          C
                                                                                                                          CD
                                                                                                                          OJ
                                                                                                                          o
                             Figure 4.8.   Schematic diagram of  the heated  box required for
                                           dilution interface sampling.
                                                                                                                            uo
                                                                                             v£> O\
                                                                                             co.
                                                                                             co-e-

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                                                                Section No. 3.16.4
                                                                Date June 30, 1988
                                                                Page 18                 S~\

obtained for the audit samples prior to analysis of the field samples.                  >—'

4.3.8   Adsorption  Tube Sampling - Adsorption  tube sampling can be  used for those
organics specified  in the Method Highlights Section,  Table B, and  for  other com-
pounds  as  specified in  the  National Institute of Occupational Safety  and Health
(NIOSH) methods.  The selection and use of adsorption tubes must be validated in
the laboratory  as  discussed  in Subsections 3-3 and 3-4 or through  the  use of the
literature.  This check  will  include selecting the proper adsorption material, and
then checking the capacity, breakthrough volume, adsorption efficiency, and desorp-
tion efficiency.  The adsorption efficiency can be greatly affected by the presence
of water vapor  and  other organics in, and  temperature of the stack gas.   If sam-
pling is conducted  for more  than one organic  compound,  the  adsorption and desorp-
tion efficiency checks must consider each.  Because changes  in process and control
equipment conditions  can greatly  affect  all of the parameters  stated  above,  it is
recommended as a standard operating procedure that more than one adsorption tube be
used.    The  first tube is analyzed as described in  Subsection  5.0.   If no problems
are found,  then the  second  tube  can be discarded.    If  problems with  the  first
tube's adsorption efficiency are discovered, then the primary section of the second
tube  can  still be  analyzed  and  the results  included with  those of the primary
portion of the first tube.
   Following are the recommended procedures for adsorption tube sampling:
   1.   The  sampling system is assembled  as shown  in  Figure 4.9-    The  adsorption
       tube(s) must  be maintained in a vertical  direction for sampling.   This is
       done to  prevent channeling of the  gases along  the side  of a tube.   It is
       recommended  that  the  sampling probe be eliminated  when  possible.    If  a     /*""\
       sample probe  is used,  it  should  be cleaned  prior  to its  initial  use with     f   J
       the  extraction solvent.    Teflon  tubing should be used  for the  probe and     ^—
       sample line.
   2.   Just prior   to  sampling,  break  off  the ends  of  the  adsorption  tubes  to
       provide  an   opening  at least one-half  of  the internal diameter.   Audit
       samples must  be collected on  the  adsorption tubes during  the  test program
       as described in Subsection 8.0.   Since on-site analysis  is  typically not
       conducted when  using  adsorption tubes,  it  is recommended  that  two samples
       be collected  from each of  the two audit cylinders.   This allows  the tester
       a second chance to obtain the proper value for each audit cylinder.
   3.   Prior  to sampling  and the collection  of  the  audit  samples,  the sampling
       system  must  be  leak  checked by  connecting  a U-tube H20  manometer  or
       equivalent to  the inlet  of the sample  probe or adsorption tube.   Turn the
       pump on  and pull  a vacuum of about 10 in.  of H20.   Shut off  the needle
       valve and then turn off  the pump.   The vacuum  must remain stable  for 30
       seconds.  If a leak is present, repair and recheck the system.
   4.   If the  flow  rate in the  duct varies by more than 10% during  the sampling
       period,  the  sample should  be collected proportionally.    The  proportional
       sampling procedures will be the same as  described for the bag sampling.  The
       only difference is that  instead  of using  the volume  of  the  bag as  the
       limiting factor to determine the  average  sampling rate,  the  breakthrough
       volume is the limiting factor.    If the source is a constant rate source
       (less than a  1Q%  change in flow rate for the sampling  period),  the samples
       can be collected at a constant rate.
   5.   Prepare the  field blank just  prior  to  sampling.   The  field blank  will  be
       handled in be  same  manner  as  the  field  samples and should  be  from the same     /"""N
       lot as  the other adsorption tubes.                                                I   }
   6.   The flow rate meter must have been  calibrated in the laboratory prior to

-------
                                                                     Probe
Supplemental
 Adsorption
   Tube
(as required)
                                           Rotameter
 Soap Bubble
  Rowmeter
(for calibration)
                                                       A*
  Sonic
  Orifice
                                                                                                      "o a en
                                                                                                      CD  fa n>
                                                                                                      Oft}  rt O
                                                                                                      fl>  CD ct
                                                                                                           H-
                                                                                                      M e_, o
                                                                                                      vo C 3
         Figure 4.9.   Adsorption tube  sampling  system.
                                                                                                         O
                                                                                                         -  CO
                 vo crv
                 co •
                 004=-

-------
                                                             Section No.  3• 16.4
                                                             Date June 30, 1988
                                                             Page 20

    the field  trip  as described in Subsection 2.1.  The  volume  of sample coll-
    ected must be accurately known for adsorption tube sampling.
7.  The sample run  time must be equal to or greater  than that specified by the
    applicable regulation.   During each  sample  run,  the data should be recorded
    on the sample data form  {Figure 4.3 or equivalent).
8.  At  the  conclusion  of each  run,  conduct  another  leak  check  as  described
    above.   If the system  does not pass  the  leak check, the run should be
    rejected, the leak located and repaired, and another run conducted.
9.  After completing  a successful leak  check,  remove  the adsorption  tube  from
    the holder and  seal both  ends  with  plastic caps.   The tubes  should  be
    packed lightly  with padding  to  minimize the chance of  breakage.   If  the
    samples are to  be held  for an extended period of  time,  they should  be  kept
    cool  to  reduce  the  amount of migration  of  the   organic from  the  primary
    section  to  the secondary  section.    Note:  Pack  the tubes  separately  from
    bulk samples to avoid possible contamination.
10. It is recommended, that  at  the conclusion of the  test,  the sample probe (if
    used)  be rinsed into a 20-ml  glass scintillation  vial with about 5 to 10 ml
    of the desorption solvent.   This  sample will be analyzed  as a check on the
    loss of the organic  in  the probe during sampling.   If more  than 10# of the
    total sample collected in  the  adsorption tubes is  present in the probe,  the
    samples should  be rejected or the sample catch adjusted  to  account  for the
    loss.   Alternatively, the  probe  can  be rinsed after  each  run and the rinse
    added to the desorption solvent prior to analysis.
11. At the  conclusion of  the  test program,  check all samples   to  ensure  that
    they are uniquely identified and check all  data sheets to  ensure that all
    data has been recorded.
G
                                                                                    O

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                                                                Section No. 3.16.4
                                                                Date June 30, 1988
                                                                Page 21


WATER VAPOR CONTENT

Method 4

Reference Method conducted in proper manner 	 (Handbook Section 3»3. Method
   4, Figure 4.1)

Wet Bulb/Dry Bulb

Temperature readings taken when stabilized 	
   WB Temp °C (°F)	  DB Temp °C (°F) 	
DIRECT OR DILUTION BAG SAMPLING

Apparatus

Pitot tube: Type S 	   Other 	,  Properly attached  	
Pressure gauge: Manometer 	  Other 	,  Sensitivity	
Probe liner:  Borosilicate 	Stainless  steel   ..	.   Teflon 	
   Clean  	, Probe heater (if applicable) on	  Glass wool filter
   (if applicable) in place  	Stainless steel or Teflon unions used
   to connect to sample line 	
Sample line:  Teflon 	, Cleaned  	, Heated (if applicable)  	
Bag: Tedlar 	  Other 	, Blank checked  	, Leak checked  	
   Reactivity check 	,   Retention check  	
Flowmeter: Proper range 	, Heated (if applicable)  	, Calibrated 	
Pump: Teflon coated diaphram 	,   Positive  displacement pump 	,
   Evacuated canister 	,  Personnel pump 	
Heated box with temperature control system:  Maintained at proper temperature 	
Charcoal adsorption tube to adsorb organic vapors: Sufficent capacity
Dilution equipment: N2 gas        ,  Hydrocarbon-free air 	,  Cleaned and
   dried ambient air 	,  Dry gas meter 	
Barometer: Mercury 	, Aneroid 	, Other 	
Stack and ambient temperature: Thermometer 	, Thermocouple 	,
   Calibrated 	

Procedures

Recent calibration (if applicable):  Pitot tube 	,  Flowmeter 	,
   Positive displacement pump* 	,  Dry gas meter* 	,  Thermometer 	
   Thermocouple 	, Barometer 	
Sampling technique: Indirect bag 	, Direct bag 	, Explosion risk bag 	
   Dilution bag	, Heated syringe 	,  Adsorption tube 	,
   Proportional rate 	,  Constant rate 	,  Direct interface
   Dilution interface 	

*Most significant items/parameters to be checked.

                    Figure 4.10.  On-site measurements checklist.

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                                                                Section No. 3.16.4
                                                                Date June 30,  1988
                                                                Page 22               S~\

Figure 4.10 (Continued)

Filter end of probe (if applicable) and pitot tube placed at centroid of duct (or
  no closer than 1 meter to stack wall) and sample purged through the probe and
  sample lines* 	.
Vacuum line attached to sample bag and system evacuated until the flowmeter
  indicates no flow (leakless)* 	
Heated box (if applicable) same temperature as duct* 	
Velocity pressure recorded and sample flow set 	
Proportional rate sampling maintained during run* 	
Stack temperature, barometric pressure, ambient temperature, velocity pressure
  at regular intervals, sampling flow rate at regular intervals, and initial and
  final sampling times recorded* 	
At conclusion of run,  pump shut off, sample line and vacuum line disconnected
  and valve on bag closed 	
Heated box (if applicable) maintained at same temperature as duct until analysis
  conducted
No condensation visible in bag* 	
Sample bag and its container protected from the sunlight 	
Audit gases collected in bags using sampling system*
Explosive area bag sampling: (with following expections same as above) 	
Pump is replaced with an evacuated canister or sufficient additional line is added
  between the sample bag container and the pump to remove the pump from the
  explosive area 	
Audit gases collected in bags using sampling system* 	
Prefilled bag: Proportional rate 	 Constant rate 	
Dilution factor determined to prevent condensation* ____	
Proper amount of inert gas metered into bag through a properly calibrated dry gas
  meter* 	
Filter end of probe (if applicable) and pitot tube placed at centroid of duct (or
  no closer than 1 meter to stack wall) and sample purged through the heated probe,
  heated sample line,  and heated flowmeter or positive displacement pump*	
Leak checked and partially filled bag attached to sample line 	
Stack temperature, barometric pressure, ambient temperature, velocity pressure at
  regular intervals, sampling rate at regular intervals, and initial and final sam-
  pling times recorded* 	
Probe, sample line, and properly calibrated flowmeter or positive displacement pump
  maintained at the stack temperature* 	
Sampling conducted at the predetermined rate, proportionally or constant for entire
  run* 	
No condensation visible in probe, sample lines, or bag* 	
At conclusion of run,  pump shut off, sample line disconnected and valve on bag
  closed 	
Sample bag and its container protected from sunlight 	
Audit gases collected in bags using dilution system* 	
o
Sample Recovery and Analysis

(As described in "Postsampling operations checklist," Figure 5-10)
*Most significant items/parameters to be checked.
O

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                                                                Section No. 3.16.4
                                                                Date June 30, 1988
                                                                Page 23

Figure 4.10  (Continued)

DIRECT AND DILUTION INTERFACE

Apparatus

Probe: Stainless steel 	, Glass	, Teflon 	, Heated system (if
  applicable) 	, Checked 	
Heated sample line: Checked* 	
Thermocouple readout devise for stack and sample line: Checked* 	
Heated gas sample valve: Checked* 	
Leakless Teflon-coated diaphram pump: Checked* 	
Flowmeter: Suitable range 	
Charcoal adsorber to adsorb organic vapors 	
Gas chromatograph and calibration standards (as shown in "Postsampling operations
  checklist," Figure 5-10)* 	

For dilution interface sampling only:
Dilution pump: Positive displacement pump or calibrated flowmeter with Teflon-
  coated diaphram pump checked* 	
Valves: Two three-way attached to dilution system 	
Flowmeters: Two to measure dilution gas, checked* 	
Heated box: Capable of maintaining 120°C and contains three pumps, three-way
  valves, and connections, checked* 	
Diluent gas and regulators: N2 gas 	, Hydrocarbon-free air 	,   Cleaned air _,
  Checked 	

Procedures

All gas chromatograph procedures shown in "Postsampling operations checklist"
  (Figure 5-10)
Recent calibration: Thermocouples 	,  Flowmeter 	, Dilution system
  (for dilution system only)* 	
Filter end of heated probe placed at centroid of duct (or no closer than 1 meter to
 , stack wall), probe and sample line heat turned on and maintained at a temperature
  of 0°C to 3°C above the source temperature while purging stack gas 	
Gas chromatograph calibrated while sample line purged* 	
After calibration,  performance audit conducted and acceptable* 	
Sample line attached to GC and sample analyzed after thorough flushing* 	
With probe removed from stack for 5 min, ambient air or cleaned air analysis is
  less than 5# of the emission results*	
Probe placed back in duct and duplicate analysis of next calibration conducted
  until acceptable agreement obtained* 	
All samples, calibration mixtures, and audits are analyzed at the same pressure
  through the sample loop* 	
Sample Analysis

(As shown in "Postsampling operations checklist," Figure 5-10)
*Most significant items/parameters to be checked.

-------
Figure 4.10 (Continued)
                                                                Section No. 3.16.4
                                                                Date June 30, 1988
                                                                Page 24               ^^^
If a dilution system is used, check the following:
With the sample probe, sample line, and dilution box heating systems on, probe and
  source thermocouple inserted into stack and all heating systems adjusted to a
  temperature of 0°C to 3°C above the stack temperature	
The dilution system's dilution factor is verified with a high concentration gas of
  known concentration (within 10%) 	
The gas chromatograph operation verified by diverting a low concentration gas into
  sample loop 	
The same dilution setting used throughout the run 	
The analysis criteria is the same shown as for the direct interface and in the
  "Postsampling operations checklist," Figure 5-10

ADSORPTION TUBES

Apparatus

Probe: Stainless steel 	, Glass 	, Teflon 	, Heated
  system and filter (if applicable) 	
Silica gel tube or extra adsorption tube used prior to adsorption tube when
  moisture content is greater than 3 percent 	
Leakless sample pump calibrated with limiting (sonic) orifice or flowmeter 	
Rotameter to detect changes in flow 	
Adsorption tube: Charcoal (800/200 mg), Silica gel (1040/260 mg) 	          S~*\
Stopwatch to accurately measure sample time 	                            f   j

Procedures

Recent calibration of pump and flowmeter with bubble meter 	
Extreme care is taken to ensure that no sample is lost in the probe or sample line
  prior to the adsorption tube 	
Pretest leak check is acceptable (no flow indicated on meter) 	
Total sample time, sample flow rate, barometric pressure, and ambient temperature
  recorded 	._
Total sample volume commensurate with expected concentration and recommended sample
  loading factors 	
Silica gel tube or extra adsorption tube used prior to adsorption tube when
  moisture content is greater than 3 percent 	
Posttest leak check and volume rate meter check is acceptable (no flow indicated on
  meter, posttest calculated flow rate within 5 percent of pretest flow rate)

Sample Analysis

(As shown in the "Postsampling operations checklist," Figure
*Most significant items/parameters to be checked.
                                                                                     o

-------
                                             Section No.  3
                                             Date June 30,
                                             Page 25
                                                                             1988
               Table  4.1.   ACTIVITY MATRIX FOR ON-SITE MEASUREMENTS
 Characteris tic
 Preliminary de-
  terminations
  and measure-
  ments
  Acceptance limits
If final results on
concentration basis,
determine the mois-
ture content of stack
gas

If final results on
emission rate basis,
determine moisture
content and flow
rate of stack gas
                   If process has >10%
                   variation in APave,
                   sampling must be con-
                   ducted proportionally
                   If preliminary survey
                   or information showed
                   a heating system nec-
                   essary for sampling,
                   determine stack gas
                   temperature,  Ts

                   Determine stack
                   dimensions

                   Select sampling time
                     minimum total
                   sampling time in  •>
                   applicable emission
                   standard; number or
                   minutes between
                   readings should be  an
                   integer
 Frequency and method
    of measurement
 Once each field test;
 use wet bulb/dry bulb
 thermometer, Method 4,
 or sling psychrometer
 See above for moisture
 content; for flow
 rate, once each field
 test using Method 1
 location, if possible,
 and Method 2 proce-
 dures

 Determine before
 test by measuring
 APave and range of
 fluctuation; if re-
 quired, use APave and
 AP measured during
 sampling to vary
 sampling flow rate to
 sample proportionally

• Prior to and during
 sampling
                       Prior to sampling,
                       using tape measure

                       Prior to sampling
Action if
requirements
are not met
 Complete
                                                                   Complete
                                                Complete or
                                                repeat sampling
                                                Complete or
                                                repeat sampling
                           Complete


                           Complete
(Continued)

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Table 4.1  (Continued)
                                                                Section No.  3.16.4
                                                                Date June 30,  1988
                                                                Page 26
                                                                  o
 Characteristic
  Acceptance limits
    Frequency and method
       of measurement
                        Action if
                        requirements
                        are not met
 Evacuated con-
  tainer sampling
1. Assemble system
   using Fig.  4.4;
   leakage
no
                   2. Minimum vacuum
                      of 10 in. of H20;
                      stable for 30 s
                   3. Heating system, if
                      used, between 0°
                      and 3°C above
                   4. Locate probe tip
                      at centroid of
                      stack or no closer
                      than 1 meter to
                      walls of stack

                   5. Purge probe and
                      sample system,
                      5 times system
                      volume or 10
                      minutes ,  which-
                      ever is greater

                   6. Sample propor-
                      ionally based on
                      APove and moni-
                      tored AP
Before sample collec-
tion, visually and
physically inspect
all connections

Before sample collec-
tion; use a
filled U-tube
manometer or equiva-
lent
                       Confirm prior to and
                       monitor during sam-
                       pling using tempera-
                       ture sensor(s)

                       Prior to sampling;
                       determine using stack
                       dimensions
                       Before sample collec-
                       tion;  with bag
                       unattached,  turn on
                       pump
                       Throughout sampling
Check for leaks,
repair system;
repeat check
                            Check system
                            for leaks;
                            check pump,
                            joints, and
                            valves for source
                            of leak; repair
                            and recheck

                            Adjust heating
                            system
                            Reposition
                                               O
                            Repeat purge
                            Repeat test
 Direct pump
  sampling
(Continued)
   Assemble system
   using Fig.  4.5;
   sample exposed
   components  of
   Teflon,  stain-
   less  steel,  etc;
   no  leakage
    Before sample col-
    lection,  visually
    and physically in-
    spect all equipment
    and connections
                        Check for leaks,
                        repair system;
                        replace inappro-
                        priate components
                                              O

-------
Table 4.1  (Continued)
                                                                Section No. 3.16.4
                                                                Date June 30, 1988
                                                                Page 27
 Characteristic
 Acceptance limits
Frequency and method
   of measurement
Action if
requirements
are not met
 Direct pump
  sampling (cont)
2. Follow steps 2-6
   for evacuated bag
   sampling
As above
As above
 Explosion risk
  area bag
  sampling
1. Assemble system,
   Figure 4.6 is one
   option; no elec-
   trical compo-
   nents in explo-
   sion risk area;
   no leakage

2. Leak check as
   above outside
   explosion risk
   area

3« Purge probe with
   a hand squeeze
   pump changing
   volume at least
   5 times

4. Follow steps 4
   and 6 for evac-
   uated bag samp-
   ling

5. Clear all oper-
   ations in writ-
   ing through
   Plant Safety
   Officer
As above
As above
                                          As above
                        As above
                                          As above
                        As above
                                          As above
                        As above
                                          Prior to working
                                          in explosion risk
                                          area
                        Complete
  Prefilled bag
    sampling
(Continued)
1. Assemble system
   using Fig. 4.5;
   need calibrated
   flowraeter in-line

2. Calculate accept-
   able dilution
   factor

3. Leak check bag
As above for
evacuated bag
sampling
                                          Prior to sampling
                                          Prior to  filling
As above for
evacuated bag
sampling
                        Complete
                        Repair or replace

-------
Table 4.1 (Continued)
                                                                Section No.  3.16.4
                                                                Date June 30,  1988
                                                                Page 28
                                                                  o
 Characteristic
 Acceptance limits
Frequency and method
   of measurement
Action if
requirements
are not met
  Prefilled bag
   sampling (cont)
4. Fill bag with
   known volume of
   inert gas
                    5.  Leak check system
                       at stack temper-
                       ature ,  minimum
                       vacuum of 10 in.
                       of H20, stable
                       for 30 s

                    6.  Follow steps 3~6
                       for evacuated bag
                       sampling

                    7.  Determine volume
                       of gas sampled
                       accurately
Prior to sampling;
use calibrated dry gas
meter or mass flow-
meter

Before sample collec-
tion without bag
attached; use U-tube
H20-filled manometer
or equivalent
                      As above
                      During sample collec-
                      tion; use flowmeter
                      or metering pump (max.
                      dilution 10 to 1) or
                      heated syringe, (see
                      below (max. dilution
                      50 to 1)
Complete
                                              Locate leak,
                                              repair or
                                              replace compo-
                                              nents , and
                                              recheck
                        As above
                        Complete
                                           O
  Heated syringe
   sampling -
   direct injec-
   tion
1. Check syringes
   for compound re-
   tention and re-
   action

2. Seal port to pre-
   vent inleakage
   of ambient air

3- Place needle in
   stack at sample
   point, pull and
   discharge sample
   volume three
   times
See Subsection 1.0
                                          Visually check
                                          Prior to sampling
Complete
                        Reseal and re
                        check
                        Complete
 (Continued)
                                                                                     O

-------
Table 4.1 (Continued)
                                                                Section No.  3.16.4
                                                                Date June 30,  1988
                                                                Page 29
 Characteris tic
 Acceptance limits
Frequency and method
   of measurement
Action if
requirements
are not met
  Heated syringe
   sampling - dir-
   ect injection
   (cont)
   Seal after pull-
   ing sample vol-
   ume, return to
   heating system,
   if necessary;
   monitor heating
   system tempera-
   ture

   Choose sample
   volumes to sample
   proportionally;
   monitor AP, if
   necessary (>10#
   change in flow
   over sampling
   period)

   Take second and
   third syringe
   samples at equal
   time intervals
   spanning the
   required sampling
   time in applica-
   ble emission
   standard
For each sample
collection; use
temperature sensor
Complete
                                          During sample  collec-
                                          tion;  use pitot tube
                        Repeat sampling
                                          During field test
                        Repeat sampling
  Heated syringe
   sampling -
   dilution
   method
  (Continued)
1. Follow same steps
   as for heated
   syringe - direct
   injection, except
   prefill bag (see
   steps 2-4 in pre-
   filled bag samp-
   ling) and inject
   gas in heated
   syringe through
   bag septum
As above
As above

-------
                                                               Section No.  3.16.4
                                                               Date June 30,  1988
                                                               Page 30
Table
         (Continued)
                                             o
Characteristic
                     Acceptance limits
'Frequency  and method
    of measurement
Action if
requirements
are not met
 Direct interface
  sampling
                    1. Assemble system
                       using Fig. 4.7;
                       no leakage
                   2.  Heating system
                      between 0°  and
                      3°C above T
                   3.  Set flow rate at
                      1 L/min

                   4.  Leak check system
                      at stack temper-
                      ature at minimum
                      vacuum of 10 in.
                      of H20;  stable
                      for 30 s

                   5.  Calibrate system;
                      duplicate analy-
                      ses within 5% of
                      their mean

                   6.  Analyze audit
                      cylinders;
                      results within
                      10% of true value

                   7.  Follow steps 4
                      and 5 of evacu-
                      ated bag
                      sampling

                   8.  Analyze samples
                      and conduct
                      posttest
                      calibration
 Before  sample  collec-
 tion  visually  and
 physically  inspect
 all connections

 Confirm prior  to and
 monitor during
 sampling using temper-
 ature sensors

 Prior to sampling
                                          During sampling;  use
                                          a U-tube  H20 mano-
                                          meter or  equivalent
                                          See  Subsection  5«0
                                         See Subsection 8.0
                                         As  above
                                         See Subsection 5-0
Check for leaks;
repair system;
repeat check
                                                                  Adjust
                                                                  Complete
                        Check system for
                        for leaks; repair
                        and recheck
                        Identify
                        problems; recal-
                        ibrate and check
                        Reject samples
                        and rerun test
                        As above
                        Complete
                                                                                      O
  (Continued)
                                                                                    O

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                                                                Section No. 3.16.4
                                                                Date June 30, 1988
                                                                Page 31
Table 4.1 (Continued)
 Characteristic
  Dilution inter-
   face sampling
 Acceptance limits
1. Follow all steps
  .. for direct inter-
   face sampling
   with addition
   of steps below

2. Assemble with
   dilution system
   in line, see
   Figure 4.8

3. If Teflon com-
   ponents cannot
   withstand stack
   temperature,
   heating system
   should be set to
   prevent conden-
   sation

4. Verify dilution
   system to within
   10# of expected
   value
Frequency and method
   of measurement
As above
                                          As above
                                          Prior to and during
                                          sampling
                                          Prior to sampling;  use
                                          a calibration gas
Action if
requirements
are not met
As above
                        As above
                        Adjust
                        Pinpoint problen
                        to dilution
                        system or QC;
                        repair and
                        recheck; adjust
                        dilution, if
                        necessary
  Adsorption tube
   sampling
i. Assemble system
   using Figure 4.9
                    2.  Break off ends of
                       adsorption tubes;
                       maintain in ver-
                       tical position
                       for sampling

                    3.  Follow step 4 for
                       direct interface
                       for leak check
Before sample coll-
ection, visually and
physically check all
connections

Just prior to samp-
ling; during sampling
                      As above
Check for leaks,
repair, and
recheck
                                              Complete and
                                              check
                        As above
(Continued)

-------
Table 4.1 (Continued)
                                                                Section No.  3.16.4
                                                                Date June 30,  1988
                                                                Page 32
                                                                o
 Characteristic
 Acceptance limits
Frequency and method
   of measurement
Action if
requirements
are not met
  Adsorption tube
   sampling (cont)
4. Conduct sampling
   proportionally,
   if the flow rate
   varies more than
   10%

5. Determine samp-
   ling time, >^ re-
   quirement of
   applicable
   emission standard

6. Run field blanks
                    7- Perform posttest
                       leak check as
                       above
During sampling
Repeat test
                                          Prior to sampling
                        Complete
Once each set of
samples

As above
                                                                  Complete
                                              Reject sample
                                              rerun test
             •    o
 Sample
  recovery
(Continued)
1. If applicable,
   remove samples
   from sampling
   system

2. Protect bag samp-
   les from sunlight
   and maintain at a
   temperature which
   will prevent con-
   densation

3. Analyze bag sam-
   ples within two
   hours of sampling

4. For adsorption
   tube samples,
   perform at least
   one probe rinse
   with desorption
   solvent to con-
   firm that <10% of
   sample is col-
   lected in probe
Following sampling
                                          Following sampling
Complete
                        Complete
                                          Following sampling
                                          Following sampling;
                                          analyze sample with
                                          GC
                        Complete
                        Adjust sample
                        values to
                        account for probe
                        catch
                                                                                    O

-------
                                                                Section No. 3.16.4
                                                                Date June 30, 1988
                                                                Page 33
Table 4.1 (Continued)
 Characteristic
  Sample
   logistics
Acceptance Limits
Properly label
all bags, contain-
ers, tubes, etc.
                     Record all data on
                     forms in Figs. 4.1,
                     4.2, and 4.3 and
                     5.1
Frequency and method
   of measurement
Visually check
each sample
                      As above
requirements
are not met
Complete the
labeling
                         Complete the
                         data records

-------
o
o
o

-------
                                                              Section No. 3.16.5
                                                              Date June 30, 1988
                                                              Page 1
 5.0  POSTSAMPLING OPERATIONS
        The  postsampling operations for Method 18 include preparation of calibration
 standards appropriate for the sampling technique used,  determination of desorption
 efficiency  and collection  efficiency for  adsorption  tubes  (if  used),  adsorption
 tube  sample preparation,  sample analysis,  and  determination  of;acceptable resolu-
 tion  and precision.   See Subsection 3-1.5 f°r postsampling  operations  related to
 velocity determinations and Subsection 3-3'5 for postsampling operations related to
 determination  of  the  flue gas."pr duct moisture.   Figure  5-10 at the end of this
 section provides a  checklist  for monitoring the postsampling operations.   Table 5'1
 at  the end of  the  section summarizes the  quality  assurance  activities  associated
 with  the postsampling operations.

 5.1   Preparation of Calibration Standards

        Calibration  standards  are  to  be prepared prior to sample analysis following
 the procedures  described in  the  following subsections.   Refer to Table  E  in the
 Method  Highlights Section for recommendations on the procedures suitable for selec-
 ted compounds.  Note that there are  two basic  types  of standards,  gaseous or liq-
 uid;  the type  prepared  depends on  the  type of  sample collected.   Gaseous cali-
 bration standards will be needed prior to  the  analysis  of preliminary survey sam-
 ples  collected  in glass  flasks or bags, and final  samples collected in  bags or by
 direct  and  dilution interface sampling.   There  are three  techniques for preparing
 gaseous  standards,  depending on  availability  and  the  chemical characteristics of
 the standard compound(s); gas cylinder standards  may also  be  used directly,  if the
 proper  concentration  ranges  are  available.   Liquid calibration  standards are re-
 quired  for  the analysis  of  adsorption  tube samples  from the  preliminary  survey
 and/or  the final sampling, as well as to determine  the desorption efficiency; there
 are two techniques  for preparing  liquid  calibration standards.   The concentrations
 of  the  calibration  standards should  bracket  the  expected concentrations  of the
 target  compound(s)  at the source being tested.   Specific  procedures for preparing
 and analyzing each  type of standard are described below.
        For each target compound,  a minimum of  three  different  standard concentra-
 tions are required  to calibrate the  GC.   An exception to this requirement involves
 developing relative response  factors  for each compound  to  be  tested as compared to
 a single organic compound.  Once  in  the  field,  the  GC is calibrated for all target
 compounds using the single  organic.   The validity  of this procedure must be first
 be proven in  the  laboratory  prior to the  test.  To save  time,  multiple component
 standards can be prepared and analyzed provided the elution order of the components
 is known.
       It is  recommended  that  the  linearity of  the  calibration curve  be checked
 comparing the actual  concentration  of the calibration standards  to  the  concentra-
 tion of  the standards calculated  using the standard peak  areas and  the  linear re-
 gression equation.   The  recommended  criteria for linearity ,is for  the  calculated
 concentration for each standard be within 7% of the  actual  concentration.
       After establishing the GC  calibration  curve, an analysis of  the  audit cyl-
 inder is performed as described in Subsection 8.1.   For  an instrument drift  check,
a  second  analysis  of  the  calibration  standards and   generation  of  a  second
calibration  curve is  required following  sample  analysis.   The area values for the
 first  and second analyses of  each standard must be  within  5#  of their average.  If
 this criterion  cannot be  met,  then  the sample  values obtained using  the  first and
second  calibration  curves should  be  averaged.   In addition,  if  reporting  such

-------
                                                              Section No.  3-16.5
                                                              Date June  30,  1988
                                                              Page 2

average values  for  the samples is warranted,  an  additional analysis of  the  audit
cylinder should be performed.   The average of the audit values obtained  using the
two calibration curves should be reported.

5.1.1  Commercial Gas Cylinder Mixtures - Commercial gas cylinder  mixtures can  be
used provided  that  the cylinders  have been certified by  direct  analysis and the
proper concentrations for the  emission test  can  be obtained.   Calibrate the  GC
using gas cylinders  by the following procedure:
     1. Secure the three  cylinders xnear the GC  and  remove their  protective  caps.
        Attach an appropriate regulator that is equipped with a flow control  valve
        to the lowest concentration standard.
     2. For preliminary survey sample  analysis, establish  the proper GC conditions
        based on  the  referenced  conditions in Table  D in the Method  Highlights
        Section, previous experience,  or possibly, if the plant being tested  has a
        laboratory,  the laboratory personnel.   For final  sample analysis,  establish
        the optimum GC conditions  determined  during the preliminary survey sample
        analysis.
     3. Attach a quick connect  or  equivalent,  compatible to  the  connection on the
        Tedlar bag or the interface  sample line,  to  the gas  sampling valve on the
        GC.
     k. Connect a length of Teflon tubing  to the flow control valve on  the regula-
        tor and connect the other  end,  using a compatible connector,  to the gas
        sample valve.
     5- With the gas  sampling valve in the load position  and the flow control  valve
        open,  open the  valve on  the cylinder  and adjust the  pressure regulator  to
        deliver a flow of 100cc/min through the sample loop,  determined by a  rota-
        meter or other flow  sensing device on  the  loop outlet.
     6. Allow the sample loop to be flushed for 30 seconds,  then  turn off the flow
        control valve.
     7. Allow the sample loop  to return to the same pressure that  will  be exper-
        ienced during  sample  analysis, determined with  a  manometer  or  equivalent
        connected  to  a  tee  on  the outlet  of  the  loop,  and immediately switch the
        valve to the  inject  position.
     8. Note the time  of the injection on the strip chart  recorder and/or actuate
        the electronic integrator.   Also,  record the  standard concentration, detec-
        tor attenuation factor,  chart  speed,  sample  loop temperature,  column tem-
        perature and identity,  and the carrier gas  type  and  flow  rate on the data
        form shown in Figure 5-l»   It is also  recommended that the same  information
        be recorded  directly on the chromatogram.  Record  the operating parameters
        for the particular detector being used.
     9- After the  analysis,  determine the retention time  of each standard  component
        and determine the peak  area.  Repeat the injection of the first cylinder gas
        standard until the area counts  from two consecutive injections are within 5
        percent of their average.
    10. Multiply the  average area count of the  consecutive  injections by the atten-
        uation factor to get the calibration  area value for  that  standard concen-
        tration.   NOTE:  Attenuation factors which affect the plot traced, but not
        the  area  count returned  by  an  electronic   integrator  should  not   be
       multiplied by  the average  area count.   Observe  the  effect  of  attenuation
        changes made  at  the   console of a  specific  electronic  integrator   to
        determine  the appropriate course of action.
o
o
o

-------
                                                               Section No. 3.16.5
                                                               Date June 30, 1988
                                                               Page 3
                Analysis of Method 18 Field Samples
             /&&  Analyst:  JT
Date: 	
Location:	
Type of Calibration Standard:
Number of Standards: 3	  Date Prepared:
      	  Plant:
      Sample Type:
                                              Target Compound:
                                                      Prepared By: A-
OC Used:    HP
                            Column Used: Ps>i
Calibration Data
First analysis/second analysis
Standard concentration (Cact)
Flow rate through loop (ml/min)
Liquid injection volume (tubes)
Injection time (24-hr clock)
Chart speed (cm/min)
Detector attenuation
Peak retention time (min)
Peak retention time range (min)
Peak area
Peak area x attenuation factor
Average peak area value (Y)
Percent deviation from average
Calculated concentration (Cstd)
% deviation from actual (#Dact)
Linear regression equation; slope
Sample Analysis Data
First analysis/second analysis
Sample identification
Interface dilution factor
Flow rate through loop (ml/min)
Liquid injection volume (tubes)
Injection time (24-hr clock)
Chart speed (cm/min)
Detector attenuation
Peak retention time
Peak retention time range
Peak area
Peak area x atten. factor (Aj/A2)
Average peak area value (Y)
% deviation from average (#Davg)
Calculated concentration (Cs)
(Y - b) At
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Standard 1
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Figure 5.1.  Data  form  for analysis of Method 18 field samples.

-------
                                                              Section No.  3.16.5
                                                              Date June 30,  1988
                                                              Page 4

  11.   Repeat the procedure for  the  other  standard  concentrations,  with  the high-
        est concentration analyzed last.
  12.   Prepare a plot with the standard  concentration  (Ca)  along the abscissa (x-
        axis)  versus  the corresponding calibration  area value along  the  ordinate
        (y-axis).  Perform a regression analysis to  calculate  the slope and the y-
        intercept.  Draw the least squares line on the plot.

5.1.2  Preparation and Analysts of Gaseous Standards from High Concentration Cylin-
ders - Gaseous standards can be prepared  from  high concentration  cylinder  gases by
dilution with hydrocarbon-free gas and  collection  of the diluted  gas mixture in a
Tedlar bag  (10  liters  or larger).   A  single-stage dilution  system is  used  for
dilutions up  to  about 20-fold.  For greater dilutions,  a two-stage dilution system
should be used.   It  is  recommended that a check of  the  dilution  system be  made by
analyzing a low concentration cylinder standard that is in the range of one of the
 standards prepared  by  dilution.   Prepare  the gaseous  standards, by the  dilution
technique, using the procedures that follow:
     1. Assemble  the  single-stage dilution system,  as  shown in  Figure 5-2 and/or
        the two-stage dilution system,  as  shown  in Figure  5-3,   using rotameters
        (flowmeters)   calibrated  following  the  procedures described  in Subsection
        2.1.3-   (More precise  dilutions may  be possible if  the dilution system
        utilizes  mass  flow  controllers  and  mass   flowmeters   in  place  of  the
        rotameters.)
     2. Connect the primary flowmeters  on the single-stage system to the  calibra-
        tion gas mixture and the  diluent  gas  (hydrocarbon-free).   On the  two-stage
        system,  connect the secondary flowmeters to the two diluent gas cylinders.
     3- Connect  a leakfree evacuated  Tedlar bag  fitted with  a  quick connect  or
        equivalent,  compatible to  the  connection on the actual sample  bags or the
        interface sample line, to the tee connector on  the  single-stage system or
        following the second stage of the two-stage system.
     4. Open  the  gas cylinders,  adjust all  the pressure regulators to  the  same
        pressure, and adjust  the  gas flows  to achieve  the desired  dilution ratio
        using the flow control valves.  On the two-stage system,  adjust the needle
        valve on the  high  concentration  waste  outlet so that 9Q%  of  the high  con-
        centration gas is  wasted  and 10# goes  to  the second stage.   NOTE:  Divert
        high concentration waste  to  a fume  hood or pass it  through  an appropriate
        adsorption  media to  protect  personnel  from   exposure  to  harmful
        concentrations of organic  vapors.
     5- Take periodic  readings  of the  pressure difference  between  the first  and
        second stages of the two-stage system,  as indicated by  a water manometer or
        equivalent,  to correct the flow reading from  the first  stage  to the second
        stage.   If the  flow rates of  the two stages can be balanced so that  the
        pressures are equal,  then  no  correction will  be  necessary.
     6. Disconnect the Tedlar  bag  from the dilution system before  the bag is total-
        ly full,  and  turn  off  the gases.   Label the bag to  indicate  the contents,
        the time  and  data when it  was prepared,  the identity  of the high concentra-
        tion gas  cylinder,  and the dilution ratio(s)  used.
     7- Record the ambient temperature,  the  flow meter readings, the barometric
        pressure,  and the  average first stage pressure  on the data form shown  in
        Figure 5.4.
     8. Calculate the concentration  (Cs),  in ppmv,  of  the component in the final
        gas mixture   by  the  following  formulas  for  'single-stage  and two-stage
        dilution.
o
o

-------
COMPONENT
   GAS
 CYLINDER
    DILUENT

     GAS
   CYLINDER
                                            "T" CONNECTOR
                              CALIBRATED ROTAMETERS
                                WITH FLOW CONTROL
                                     VALVES
                                        "H
                                                                          TEDLAR BAG
O OT
P fl>
Ct O

-------
                                                           MANOMETER
                                             HIGH
                                        CONCENTRATION
                                            WASTE
                               NEEDLE VALVES
                ROTAMETERS
                                       LOW
                              £»• CONCENTRATION
                                       GAS
                                                                 DILUENT AIR
         PURE SUBSTANCE OR
     PURE SUBSTANCE/N, MIXTURE
                           Figure 5.3.   Two-stage  calibration gas dilution system.
                                                  13 O to
                                                  O P CD
                                                   «-i O
                                                    og:

                                                    OJ .
                                                    O
                                                    •  OO
                                                                                                     OS-
                                                                                                     OOVJI
O
O
O

-------
                                                              Section No. 3.16.5
                                                              Date June  30,  1988
                                                              Page 7
           Preparation of Standards by Dilution of Gas Cylinder Standards
Date:
2/Z-t/
             Preparer:
                                                Purpose:
Cylinder Component :
                                                 Source:
                    _            _
Component Concentration  (X) :  
-------
Section No. 3.16.5
Date June 30, 1988
Page 8
                                                                                     o
For single-stage dilution:


                                    (X x qc)
                              Cs = 	                       Equation 5-1


   where

             X    = Mole or volume fraction of the organic in the calibration gas
                    that was diluted, ppmv,
             qc   = Flow rate of the calibration gas that was diluted, and
             qd   = Diluent gas flow rate.

For two-stage dilution:

                        1c2 corr = <*c 2 actual X ~	~             Equation 5-2


   where

   ^c2 corr    = Corrected flow rate from the first stage to the second stage,
   qc2 actual   = Actual flow rate from the first stage to the second stage,
   Pd           = Average differential pressure  between the first and second          j^*\
                 stage, mm or in. H20, and                                            f  j
   Pb           = Barometric pressure,  mm or in.  H20.                                  X_x

   and
                          "c1           ^c 2  corr
   Cs           = X x  	 x 	                Equation 5-3
                      (qcl  * qdl)   (qc2 corr +  qd2)
   where

    X          =  Mole or volume  fraction of the organic in  the  calibration gas
                  that was diluted,
    qcl         =  Flow rate of the calibration gas diluted in the first stage,
    qdl         =  Flow rate of the diluent gas in the first stage, and
    qd2         =  Flow rate of the diluent gas in the second stage.

   9.  Prepare two more  calibration standards from  the high  concentration cylin-
      der  gas  sufficient  to bracket the expected  concentration in the source
      samples.
  10.  Analyze  the  calibration  standards  following  the  procedures  described in
      Subsection 5«1«1 for  commercial gas cylinder mixtures.  Use  a  pump on the
      outlet side of  the sample loop to flush the  standards  through  the loop at
      100  cc/min  for  30 seconds.   Using a manometer  connected  to  a tee on the
      outlet of  the  sample loop,  make  certain  that the  sample  loop  pressure
      during analysis of the calibration  standards  is  equal  to  the  loop pressure
      during actual sample analysis.
  11.  Once the  calibration curve is established, it is recommended,  if available,
      that an undiluted cylinder  standard in the range of the standard  curve be
      analyzed  to verify the dilution ratio.  Analyze  the cylinder  and  calculate
      the  sample  area value by  multiplying the  peak area  by  the  attenuation
                           O

-------
                                                              Section No. 3.16.5
                                                              Date June 30, 1988
                                                              Page 9

        factor.  Use the slope  and  the  y-intercept derived from the linear regres-
        sion equation and  the sample area value to  calculate  the cylinder concen-
        tration (Cs) by the following formula:
                                         Y - b
                                    C. =
Equation 5-4
     where
                  Y = Sample peak area, area counts,
                  b = y-intercept of the calibration curve, area counts, and
                  S = Slope of the calibration curve,  area counts/ppmv.

The  calculated concentration  of  the  undiluted  cylinder standard,  based on  the
analysis and the calibration curve generated  from the diluted standards,  should be
within 10% of the true value of the undiluted cylinder.  If this criteria cannot be
met, then the  GC  calibration  should be checked,  the  diluted  sample may be outside
the  calibration  range,  or  there  is  a problem  with   the  dilution system  used to
prepare the standards (e.g.  the rotameters are out of calibration, etc.)-   Identify
the problem and correct  it, or use one of the other approaches for preparing cali-
bration standards.

5.1.3  Preparation  of Calibration Standards by Direct Gas Injection -  This proce-
dure is  applicable  to organic compounds  that exist  entirely as a  gas at ambient
conditions.   The standards are prepared by  direct injection  of a known quantity of
a "pure" gas standard into a 10-liter Tedlar bag containing 5-0 liters of hydrocar-
bon-free air or nitrogen.  If there is more than one  target  compound then multiple
component standards  can  be  prepared by this  method provided  the  relative elution
pattern for  the  compounds is known for the GC  column being used.   The  following
procedures are used to prepare standards by direct gas injection:
     1. Evacuate  a  previously leak checked,  leakfree 10-liter  Tedlar bag  (also
        checked for  zero retention) equipped  with a  quick  connect  or  equivalent
        compatible to the connection on the Tedlar bag or the interface sample line
        and preferably fitted  with a septum-capped tee at the bag inlet (see Figure
        5-5).
     2. Fit a  septum to  the  outlet of  the gas  cylinder containing the  standard
        component.
     3. Meter 5-0 liters  of  hydrocarbon-free air or nitrogen  into the bag  at a rate
        of 0.5 liter/min  using a  dry gas meter that has been  calibrated  in a manner
        consistent with the  procedure  described in Subsection 2.1.2.   At the start,
        record dry gas meter pressure  and  temperature.
     4. While the bag  is filling, fill and purge a 0.5-ml gas-tight syringe  with
        the  standard  gas by  withdrawing  the  gas  from the  cylinder through  the
        septum.  Repeat the  fill  and purge of the syringe  seven times before final-
        ly filling the syringe and capping the needle with a  GC  septum.   Allow the
        syringe temperature  to equilibrate with the ambient temperature.
     5. Immediately  before  injecting  the gas  into the  bag  through the  septum,
        remove the  septum cap,  and adjust the  syringe to the  desired volume  by
        expelling the excess gas.   The syringe should now be at ambient  pressure.
        Inject the gas into  the bag through the septum (through the side of the bag
        if it has not been fitted with a  septum), withdraw the syringe,  and  imme-
        diately cover any resulting hole with a piece of masking tape or  the  equi-
        valent .

-------
             Nitrogen
             Cylinder
                                                                          Gas
                                                                          Tight
                                                                         Syringo
                                   Dry Gas Motor
                                                                                        Soptum
                                                                                        TedlarBag
                                                                                        Capacity
                                                                                        10 Liters
                                                            T) O Cfl
                                                            (3 p 
-------
7.

8.
                                                              Section No. 3.16.5
                                                              Date June 30, 1988
                                                              Page 11

        Record  the  final  dry  gas  meter  temperature  and  pressure,  turn  off  the
        dilution  gas,  and  disconnect  the  Tedlar  bag;  record  the  ambient
        temperature  and pressure on  a data form such  as the one  shown in Figure
        5.6.
        Place  the bag on  a smooth  surface,   and  alternatively depress opposite
        sides of the bag 50 times to mix the gases in the bag.
        Calculate  the  organic standard concentration  in the bag (Cs ) in ppmv using
        the following  formula.
                          x 106
                             293 x ps

                             T  x 760
                                                           P. x T
Gv x 103 x
           C_  =
                              293
                                                                      Equation 5-5
                          y x
                                 x 760
                                    103
where
                Gv  = Gas volume  of  organic compound injected into the Tedlar bag,
                      ml,
               106  = Conversion  to ppmv, ul/liter,
               Ps   = Absolute pressure of  syringe before injection, mm Hg,
               Ts   = Absolute temperature  of the syringe before injection, °K,
               Vm   = Gas volume  indicated  by dry gas meter, liters,
               y    = Dry gas meter correction factor, dimensionless,
               Pm   = Average absolute pressure of the dry gas meter, mm Hg,
               Tm   = Average absolute temperature of dry gas meter, °K, and
               lO3  = Conversion  factor, ml/L.

        Note: The syringe pressure  and absolute temperature should equal the baro-
        metric pressure and the absolute ambient temperature.
     9. Prepare two more calibration standards sufficient  to  bracket the expected
        concentration in the source samples.
    10. Analyze  the  calibration  standards  following  the procedures  described in
        Subsection 5-!•!  for  commercial gas cylinder mixtures.  Use  a pump on the
        outlet side of  the  sample loop to  flush the standards  through the loop at
        100  cc/min  for  30 seconds.   Using a manometer  connected  to a  tee  on the
        outlet of the  sample loop,  make  certain  that  the  sample  loop  pressure
        during analysis of the calibration  standards is  equal to the loop pressure
        during actual sample analysis.

5.1.4  Preparation of Calibration Standards by Liquid Injection - This procedure is
used to  prepare  gaseous  standards  in Tedlar bags  from liquid  organic  compounds.
The liquid compounds used must be 99 • 9% mole pure  or the purity must be  known to
calculate the gaseous  standard concentrations.   If  there is more  than  one target
compound, then multiple component standards can be prepared by this method provided
the relative  elution  pattern for the compounds is  known  for the  GC  column being
used.   Use the procedure that follows to prepare standards by this  technique.
     1. Assemble  the equipment shown in Figure 5«7 using a dry gas  meter calibrated
        following the procedure described in Subsection 2.1.2 and a water manometer
        for the pressure gauge.   All  connections,should  be  glass,  Teflon,  brass or
        stainless steel  with quick connects  or equivalent,  compatible to the con-

-------
                                                               Section No. 3.16.5
                                                               Date June 30, 1988
                                                               Page 12

        Preparation of Standards  in Tedlar Bags by Gas and Liquid Injection
                                                                                     o
Date:
                   Preparer:
                                              Purpose:  C*libr-e>hb*
                                                                          held £$-/•
Organic Compound:
Compound Source:
                                                         Gas:
                                                                  or Liquid:
                       Compouhd Purity  (P) ;
                                                     Compound Mole Weight (M) :  /£*>. 83
      Gas Injection
Bag number or identification
Dry gas meter calibration factor ,(Y)
Final gas meter reading, liters
Initial gas meter reading, liters
Volume metered (Vm), liters
Ambient temperature, °C
Average gas meter temperature, °C
Absolute gas meter temp. (Tra), °K
Barometric pressure  (Pb), mm Hg
Average gas meter pressure, mm Hg
Absolute gas meter press. (Pm), mm Hg
Gas volume injected  (Gv), ml
Syringe temperature  (T8), °K
Absolute syringe pressure (P ), mm Hg
Calculated concentration (Cs)
                                         Mixture 1
                    T  x P
                    1s x rra
              v
                                                       Mixture 2
                                                         A//A-
                                                                      Hixture 3
                                                                        MM
                                                               s  c a 1 c .
                                                    a  c o r r .
                                                                    x loo*
                                                                                        O
      Liquid Injection
  Bag number or identification
  Dry gas meter calibration  factor  (Y)
  Final gas meter reading* liters
  Initial gas meter reading, liters
  Volume metered (Vm ) , liters
  Average gas meter temperature, °C
  Absolute gas meter  temp. (Tm), °K
  Barometric pressure (Pb ) ,  mm Hg
  Average gas meter pressure, mm Hg
  Absolute gas meter  press.  (Pm), mm Hg
  Liquid organic density  (p) , ug/ml
  Liquid volume injected  (Lv), ul
  Calculated concentration (Cs )
                                      Mixture 1
                                         S-l
                                        17-.2&
                                         Z-K
                                         AS"
                                        3->00
                                        3-1,?-
  Cs  = 6.24 x 10* x
                       Lv x p x T0
                                                       Mixture 2
                                                          3-Z
                                                           1.10
                                                         7-.00
                                                         2,6
                                                        30!
                                                           . 4-
                                                          /.«#-
                                                        /.6.Z3
                                                         Z.00
                                                           J.4-
                                                                      Mixture 3
                                                                         S-3
                                                                        O- 9430
                                                                       ze.qo
                                                                         2-6
                                                                        75-6,4
                                                                         /.I
                                                                        2.00
                                                                         /4-.S"
                                                               s  caic
                                                                    x 1002
                     M x Vm x y x Pm
Figure 5-6.  Calibration data  form for preparation of  standards  in Tedlar bags  by
             gas and liquid injection.
                                                                                      o

-------
                                                                     SYRINGE
•N
                                                                      s
                                                                        If
               NITROGEN CYLINDER
  SEPTUM



MIDGET IMPINGER
                                                                 -p:
             TEDLAR BAG

            ,  CAPACITY

              50 LITERS
                             Figure 5-7-   Apparatus for preparation of calibration  standards  by liquid

                                          injection.
                                                                                                               TJ O 03
                                                                                                               to ta n>
                                                                                                               03 rt o
                                                                                                               (D (D ct
                                                                                                                   H-
                                                                                                               »-» e-i O
                                                                                                               W   3
                                      OJ .
                                      o
                                      -  OJ
                                                                                                                VO O\
                                                                                                                oo •
                                                                                                                OOU1

-------
                                                          Section No. 3-16.5
                                                          Date June 30, 1988
                                                          Page 14

      nection on the Tedlar bag or the interface sample line, for connection to
      the Tedlar bag.
   2. Allow  the  liquid organic  compound to  come  to ambient  temperature,  and
      determine  the  density of  the  liquid by  weighing the liquid  in a tare-
      weighed  ground-glass stoppered  25-ml  volumetric flask or ground-glass
      stoppered  specific  gravity bottle.   Calculate the  density in  terms of
      g/ml.   As  an alternative, use a literature  value of  the  density of the
      liquid at 20 °C.
   3. Leak check the  system by pressurizing it to 5 to 10  cm  (2 to 4 in.) H20
      and shutting off  the diluent gas supply.  The system is leakfree if there
      is no  change in  the pressure after  30 seconds.    If the  leak  check is
      good,  release  the pressure.  !lf the  system  fails the leak check, locate
      the leak using a soap solution and repair the leak.
   4. Connect  a  quick connect  or  equivalent, compatible to  the connection on
      the Tedlar bag or the interface sample line,  to a leakfree uncontaminated
      50-liter Tedlar bag.  Evacuate the bag.            "  .
   5. Turn on the hot plate and bring the water to a boil.
   6. Connect the bag to the impinger outlet.
   7. Record  the initial  meter reading and  temperature.    Open  the diluent
      supply valve,  and adjust the flow rate to about  3  liters/minute so that
      the bag will fill  in about  15  minutes.   Record the  meter pressure and
      temperature and  the barometric pressure  at  the  start on  a form such as
      the one shown in Figure 5-5-
   8. Use a  clean 1.0- or 10-microliter syringe  with  a needle of sufficient
      length to inject  the liquid below  the air inlet branch of the tee on the
      midget impinger.
   9. Fill  the syringe  to the  desired volume with the  organic  liquid,  and
      inject  the liquid by inserting  the  needle through the  septum until the
      needle is  below the air  inlet.   Depress the  syringe plunger completely
      over a period  of about 10 seconds and withdraw  the  needle.   NOTE:  When
      dispensing liquid from a  syringe,  take  care  to account for the volume of
      liquid present  in the syringe needle.   In general,  the potential error
      resulting from  the  volume of the  needle  is  most  conveniently avoided by
      ensuring  that  the   needle  volume  is  completely  full  of liquid  upon
      filling the syringe  and dispensing from it.   If air pockets exist in the
      syringe after filling, this will be almost impossible.
  10. When the bag is almost filled, record the water manometer pressure.  Turn
      off the diluent gas  supply,  and  disconnect the bag.   To equilibrate the
      contents in the bag, either set  the bag aside for an hour or massage the
      bag by alternately depressing opposite sides  of the bag 50 times.
  11. Record  the  final meter  reading  and  temperature.   Calculate  the  con-
      centration of the calibration standard  (Cs)  in the  bag in  ppmv using the
      following formula.


      — x p x 24.055 x 106
      M                                       Lv x  p x Tn
Cs = 	 =  6.24 x 10" x 	     Equation 5-6
              293 x Pm                      M x Vm  x y x Pm
     Vm  x Y x 	 x 103
              Tm  x 760
O

-------
                                                          Section No. 3-16.5
                                                          Date June 30, 1988
                                                          Page 15

where
         Vra     = Gas volume indicated by dry gas meter, liters,
         Lv     - Volume of liquid organic injected, ul,
         M      = Molecular weight of the organic compound, g/g-mole,
         p      = Organic liquid density, g/ml,
         24.055 = Ideal molar  gas volume  at  293 °K  and  760 mm  Hg,  liters/g-
                  mole,
         106    = Conversion to ppmv, ul/liter,
         103    = Conversion factor, ul/ml, and
         y      = Conversion factor for dry gas meter.

12. When using  a liquid  standard that  is not 99-9#  pure,  use  the following
    formula to correct the calculated concentration of the calibration standard
    (C« „„„) in ppm .
                                      c al c
                                           X P
                                                                     Equation 5-7
 where
          s c or r
         i
         •'s c a 1 c
                      = Corrected calibration standard concentration, ppmv,
                      = Calculated  calibration  standard concentration  (Cs),  ppmv,
                        and
             P        = Purity of liquid organic compound, percent.

    13. Prepare  two  more  calibration standards sufficient  to bracket the expected
        concentration in the source samples.
    14. Analyze  the calibration  standards following  the procedures  described in
        Subsection 5»1«1  for commercial gas cylinder mixtures.   Use a pump on the
        outlet side  of  the sample loop to  flush the  standards through the loop at
        100  cc/min for 30 seconds.   Make certain  that  the  sample loop pressure
        during analysis of the  calibration standards is equal to the loop pressure
        during actual sample analysis.
    An  alternative procedure,  subject  to  the  approval  of the  Administrator,  for
preparing gaseous  standards  from  liquid organics  substitutes  a heated GC injection
port for the midget impinger setup and, due to the high back pressure of the injec-
tion port, a calibrated mass flowmeter for  the dry gas meter.

5.1.5   Development of  Relative Response  Factors  and Relative  Retention Factors-
Far emission tests where  on-site  GC analysis involving more  than one organic com-
pound will be  conducted,  the development and use of  relative response factors and
relative retention times  is recommended.   In the laboratory,  gaseous calibration
standards are prepared for each target  organic  compound and analyzed by one of the
techniques described in the previous subsections.   Choose one of  the  target com-
pounds or prepare  and  generate another calibration  curve for  a different organic
compound to be used to calculate the relative response factors and retention times.
The compound  selected  should  exhibit  a  retention  time comparable to  the  other
target compounds,  should  be stable, and/or easy to  prepare and  use in  the  field.
This procedure must be verified in the laboratory prior to field testing.
    The relative response factors  are calculated by dividing  the slopes of  the
target compound  calibration curve by  the  slope  of  the selected organic calibration
curve.   The y-intercept from the  regression equation  is ignored in calculating the
relative response  factors.   It  should  be noted that  a  very  large  y-intercept

-------
                                                              Section No. 3.16.5
                                                              Date June 30, 1988
                                                              Page 16

(greater than 5%  of  the slope)  for any compound may  adversely affect the validity
of  this  calibration  technique.   During  analysis  of  field samples,  the selected
organic  compound  can  be used  to calibrate  the  GC  detector response  and column
performance.  The response  factor determined  in the  field for the selected organic
is  used  to calculate the  field  response factors for  the other  target compounds
using the  relative response factors determined previously  in  the  laboratory.   The
same approach  is  used  to predict the retention times  of  target  compounds in the
field using  the selected compound retention  time  determined in the  field and the
relative retention times for the target compounds determined in the laboratory. Use
the following procedures to develop relative response  factors  and relative reten-
tion times.
     1. Generate,  at  the minimum, a three-point calibration  curve for each target
        organic compound using gaseous standards following the procedures described
        in the preceding subsections.  Record the retention time of each compound.
     2. Select  one of the  target compounds,  preferably with a  retention time be-
        tween the  other target compounds,  or generate another  calibration curve,
        with a  minimum of  three  points,  for  a non-target  organic  compound with a
        comparable retention time.  Select  the standard compound to be used in the
        field based primarily on  the ease of  use.  Determine the retention time of
        the selected compound (if not already determined).  Measure the carrier gas
        flow rate using a bubble-type flowmeter or other suitable flowmeter.
     3. Inject a sample of  the diluent gas,  and determine the retention time of the
        unretained diluent  peak.   This is needed to  calculate  the relative reten-
        tion by the following formula:
                  * "R x i
          rx/s - 	                                         Equation 5-8


     where

          rx/« = Relative retention time based on adjusted retention volumes of the
                 target compounds and the selected compound, cc/cc,
          tRxi = Initial retention time of compound x, seconds,
          tM1  = Initial retention  time of unretained  diluent gas  peak,  seconds,
                 and
          tRgl = Initial retention time of selected organic compound, seconds.

     4. Calculate the relative response factor for each target compound relative to
        the compound selected in step 2 using the following formula.


             FRx = —                                                  Equation 5-9

     where

             FRx = Relative response factor for compound x, dimensionless,
             ms  = Slope from  the  calibration  curve regression  equation  for  the
                   selected organic compound,  area counts/ppmv, and
             mx  = Slope from the calibration curve regression equation for
                   compound x,  area counts/ppm .
o
 /"""N
 O

-------
                                                              Section No. 3-16.5
                                                              Date June 30, 1988
                                                              Page 1?

         To verify  that the  relative response  factors  are  correct,  simulate the
         transportation of the GC to  the  field  by turning off the detector, the GC
         oven  and the  carrier gas flow overnight or longer.   After the simulated
         period  has  elapsed,  turn on the GC, the carrier gas, and the detector, and
         establish the  analytical conditions that were used  to generate the  relative
         response factors.  Measure the carrier  gas  flow rate.
         Recalibrate the GC by generating a three-point calibration curve using the
         selected organic compound,  analyze each of the target compound calibration
         standards,  and a diluent gas sample.   Calculate  the concentration of each
         target  compound using the relative  response factor  for the compound and the
         slope  from  the  new  calibration  curve  determined for the selected organic
         compound with  the  following formula.
                          x F,
                             Rx
                                                             Equation 5-10
                     m
     where
                      s t d
                   =  Calculated  concentration of compound x calibration standard,
             m
              s td
           =  Detector  response  for compound x  calibration standard, area
              counts,
           =  Slope  from  new  calibration  curve  generated  for  selected
              organic standard compound, area counts/ppmv,  and
     ^"RX   =  Relative response factor for compound x, dimensionless.
The calculated value for each target compound using the compound's relative
response factor must be within  5% of the actual standard concentration for
this technique to be used for that compound.
Determine  the predicted  retention  times  for  the target  compounds using
their relative  retention times and  the retention  time  determined for the
selected organic compound using the following formula:
                T x f
                    = ' '
                         T s t
                               M f
                                                                      Equation 5"
     where
        Txf
        ?sf
                      Calculated  retention  time for compound  x using the relative
                      retention time factor, seconds,
                      Measured  retention  for  selected  organic  compound  during
                      second analysis , seconds , and
               tMf  = Measured retention time of unretained diluent gas peak during
                      second analysis, seconds.
        The calculated retention  time  for the target compounds should agree within
        one second or  2%,  whichever is greater, of  the  actual retention time seen
        for the target compounds during the second analysis.
     8. Record all data on a form such as the one shown in Figure 5-8.

5-1.6   Calibration  Standards for Adsorption  Tube  Samples - The calibration stan-
dards necessary for  the  analysis  of adsorption tube samples differ from the stan-
dards described in the previous subsections in that the adsorption tube standards
are liquid rather than gaseous.   The liquid standards can be  prepared directly in
the desorption  solvent  following  the  procedures described  in  the  methods  refer-
enced in Table F or,  subject to the approval of the Administrator, on blank adsorp-

-------
                                        .                       Section No. 3-16.5
                                                               Date June 30, 1988
                                                               Page 18

       Development of Relative Response Factors and Relative Retention Factors
                               o
Date: ^-/Z-k /6& Preparer: \7- C?oo
Target Compound: Perch 1 or o eft** Lu/^J-.
Surrogate Compound: -Lsotyui^*^-

Target Compound Calibration Data
First analysis/verify analysis
Standard concentration .uL. '
Flow rate through loop (ml/min)
Liquid injection volume (tubes)
Injection time (24-hr clock)
Chart speed
Detector attenuation
Peak retention time (tRxi/tRxf)
Peak retention time range
Peak area
Peak area x atten. factor (Yi/Yx
Verification analysis conc.(Cx)
Percent deviation from actual
Calculated retention time (rTxf)
Percent deviation from actual
Linear regression equation; slope
Surrogate Calibration Data
First analysis/second analysis
Standard concentration
Flow rate through loop (ml/min)
Liquid injection volume (tubes)
Injection time (24-hr clock)
Chart speed
Detector attenuation
Peak retention time (tRsl/tRsf)
Peak retention time range
Peak area
Peak area x attenuation factor
fJrSc-1^- Purpose
Type of Standard
Type of Standard

Standard 1
_^.05>^
T.OO! tCQ
/V/f- / /l/4
)4'.CO/ /4:3'
/O&H/P'l*/ 10
Z. 1 -z-
/Z..43/ 2.,4-S
O.02-
39.3 / 34^
) 74O / (#2,
?. l^"
—l/,t%
2..4-Z
-0.07,
(mx): 73.38

Standard 1
/o-o,^
JLOO/^ 3JJO
f/A-l tifi
I4:oi/ /4-:2Lfc
ijfc / * / tD
1 1 }
'Z.ldl 3.2£>
O.O2-
7^3 / ^f
*7fc 3 / ?(**}
Linear regression equation; slope (m0 ) : <74-39 (m, ):

Nonretained peak retention time (tM1
Relative Response Factor (FRK): /. 2


/tnf): O.t\ /O.

•J- Relative Retei

: UUL Q>»™™*H«
: l-lquitl ,'r> B»Q
: C^ds Cif lt'ndJ&-
'
Standard 2
67.7-
2-OO / zoo
A/A-/ MAr
f5:t>*>/ /5".'4O
10 1 10
2. 1 2.
2.. 44 1 2, 4-5"
0.03
Wit/ /?&3
3 62^/39 2 4-
5-2.4-
+1.4
3..4-1-
O.(f7»
y-intercept (b)
Standard 2
SO-O^M
000/2^70
AJ fir/ fit A
/4,1 &/ /S'12,
/o //o
/ / 1
3.27/3.2.6
O.Ol
3-7&(o/ 3-W4-
!-•?(,&/ j-j-q 4-
&v*i't>L>(* rntxjiz



Standard 3

Z.QO! 2-QD
A/A- 1 A/-4
/4 .'/B//^:^
10/10
2-1 2-
Z.4-4/ 3,4-Z-
0.02.
?>(f52l $(e(*1e>
73o<-/7332-
-/.4
2.4-1.
0>(e"?t>
: lO.^tf

Standard 3
/CO ff>H\
300/2.00
/JAJ X/A
l^'All tb'&l
/O 1 /f
2.1 2-
3.11 / S.1(f
O-OI
4?l(p/4?£2-
1432./ VSO*
9£~./0 y-intercept (b) : -/6.0C

43

ntion Factor (rx/


,.): 0.1-

                                                                                     O
                       -x/s
                 'Txf
                                    -  tM.)
                                  i  -  tM1)
                                                           x F,
                                                              Rx
m
                                                       s t d
                                   f)  x rx/s)  + t,
"Mf
                              O
Figure 5-8.  Data  form for development of relative  response  and relative retention
             factors.
                                                         'T>'.-,

-------
                                                              Section No. 3-16.5
                                                              Date June 30, 1988
                                                              Page 19

 tion  tubes  and then desorbed.   Both methods require similar preparation and analy-
 sis  of standards  and  desorption efficiency samples,  but the way  the calibration
 curve  is generated is different.
    For  calibration standards  prepared  directly  in  the desorption  solvent,  the
 standards are  used to generate the calibration curve, and the desorption efficiency
 is  determined separately.   The calculated desorption  efficiency is  then  used to
 correct the analytical  results  for  the emission test samples.   The disadvantage of
 this  method is that the desorption efficiency may not  be constant for each level.
 This  can result  from a constant amount of analyte being retained by the adsorbent,
 instead of  an  amount proportional to the total amount of analyte on the adsorbent.
 When using  the desorption efficiency to correct each analytical result, the analyst
 must  use  the desorption efficiency determined for  the  concentration level closest
 to that of  the sample.
    For  calibration standards prepared  on absorbent material,  the  desorbed solu-
 tions  are used to generate the calibration curve.   By this procedure, the desorp-
 tion  efficiency  is already taken into  account when calculating the organic compound
 catch  of  the  adsorption  tube samples.  Liquid calibration  standards  must also be
 prepared to calibrate  the GC to determine  if  the  desorption efficiency is greater
 than  50#.   The  advantage of this  method is that  both  level-dependent or absolute
 amounts  of   organic compounds not  desorbed from  the adsorbent  are automatically
 taken  into  consideration.
     For  maximum  accuracy,  preparation  of standards  directly  in  the desorption
 liquid or on adsorbent will  require the preparation of a relatively large volume of
 a  high concentration  working standard  from which  the calibration  standards  are
 prepared.   The working  standard  should be 100  times more concentrated than the
 highest concentration calibration standard.  Three levels of calibration standards
 should be prepared to bracket  the  expected concentration of  the liquid resulting
 from  desorption of actual  samples.   The  concentration  of the  sample desorption
 liquid will depend on the catch weight of the target  organic compound(s)  and the
 amount of desorption liquid used (1.0 ml per  100 mg of  adsorbent material).   The
 catch  weight will  in turn depend on  the sample volume of flue or  duct  gas drawn
 through the tubes  and  the concentration of the emission source.   Use the following
 formula to  estimate the  concentration  (Cs),  in ug/ml,  of the midrange liquid stan-
 dard that will be  approximately equal  to the actual samples:

                                      Vpr«. X Cc X M
                                 Cs  =	                   Equation 5-12
                                       24.055 x Ld
 where

     Vpred   = Predicted gas sample volume, liters,
     Cc      = Concentration of the organic compound at the source, ppmv
               (ug-moles/g-mole),
     M       = Molecular weight of organic compound, ug/ug-mole,
     24.055  = Ideal molar gas volume at 293 °K and 760 mm Hg, liters/g-mole, and
     Ld      = Volume of desorption liquid, ml.

The preliminary  survey  sample  results should  be  used  to  calculate  the  required
calibration standard concentrations.
    To prepare adsorption tube standards, use the procedure described in the refer-
enced  method or the alternative procedure,  subject to  the  prior approval  of  the
Administrator.   Regardless of which type of calibration  standard is  selected,  use
the following procedures to prepare  the standards:

-------
                                                              Section No. 3.16.5
                                                              Date June 30, 1988
                                                              Page 20

     1. Prepare a working  standard for each organic compound by weighing each com-
        pound into an individual tare-weighed ground-glass stoppered 250-inl volume-
        tric flask.  Dissolve  the  compound in the proper desorption solvent speci-
        fied by the  referenced method  in  Table E of the Method Highlights Section.
        Dilute the solution to volume.  Refrigerate  the  working standard when not
        being used.
     2. Using a clean  microliter syringe, transfer the required amount of working
        standard to  a vial equipped with  a Teflon-lined septum top,  and add suffi-
        cient desorption solvent to achieve a final  volume  equal  to the volume of
        desorption solvent required for  actual  samples.    Cap  the vial  with the
        top, shake the vial to mix  the contents.  NOTE: When dispensing liquid from
        a syringe,  take care  to account  for  the volume  of liquid  present in the
        syringe needle.  In general, the  potential error resulting from the volume
        of  the  needle  is  most  conveniently avoided by  ensuring that  the needle
        volume is completely full of liquid upon  filling the syringe and dispensing
        from it.   If air pockets exist in  the syringe  after filling,  this will be
        almost impossible.
     3- Establish the  optimum  GC conditions determined during  the analysis of the
        preliminary  survey samples.
     4. Select  a  suitably  sized injection  syringe  (5- or  10-ul),  and  flush the
        syringe with acetone  (or   some other suitable solvent  if acetone  is the
        standard component) to clean the syringe.
     5. Flush the  syringe  with standard solution by  withdrawing a syringe full of
        the  solution from the  septum vial,  and dispensing  the  solution  into  a
        beaker containing  charcoal  adsorbent.
     6. Refill  the  syringe with standard  solution, withdraw the  syringe from the
        vial, and wipe the syringe  needle with a  laboratory  tissue.
     7. Adjust the syringe volume  down to the desired  amount  (see NOTE under Step
        2), and inject  into the GC.   Note  the time  of the  injection  on the strip
        chart recorder  and/or  actuate  the electronic integrator.  Also, record the
        standard concentration, detector attenuation  factor, chart speed, injection
        port temperature,  column temperature and  identity, and the carrier gas type
        and flow rate on the form shown in Figure 5-9-  It is also recommended that
        the same information be recorded  directly on the chromatogram.  Record the
        operating parameters for the particular detector being used.
     8. After the analysis,  determine  the retention time of the standard component
        and  determine  the peak area.  Repeat  the  injection of the  first liquid
        standard until  the area count from two  consecutive injections  yield area
        counts within 5 percent of  their average.
     9. Multiply the average area count of the consecutive injections by the atten-
        uation factor  to get the calibration  area  value  for that standard concen-
        tration .
    10. Repeat the procedure for the other standard concentrations.
    11. Prepare a plot with  the  standard  concentration  (Cs)  along the abscissa (x-
        axis) versus the  corresponding calibration area values  along  the ordinate
        (y-axis).   Perform a regression analysis  to calculate  the  slope and the y-
        intercept.   Draw the least squares line on the plot.
    To  determine  the  desorption  efficiency  for the  target  organic  compound(s)
requires spiking  the target organic compound(s) onto  the  absorbent  material and
desorbing the compound(s)  using the same procedures  that will be used  for actual
samples; the desorption solution is then  analyzed.   The spikes  should be prepared
at three levels in the  range of the source  samples.  The  following procedures are
used to determine the desorption efficiency:
o
o
o

-------
    8
                                                         Section No. 3-16.5
                                                         Date June 30, 1988
                                                         Page 21

1. Place  an amount of  adsorbent material equivalent  to the amount  used for
   actual tube  samples  in  a vial with a Teflon-lined septum cap.   Prepare ten
   vials  (three sets of triplicates and one blank).
2. Using  a  clean  microliter syringe,  aliquot from  the  working  standard solu-
   tion,  in triplicate into each set of vials,  an amount of  spike  equal to
   each level of calibration standard.
3- Cap each vial  immediately after spiking,  and allow  the  vials  to sit undi-
   sturbed  for the 30 minutes.
4. To desorb the ".spiked organic  compound(s), dispense  the  appropriate volume
   of desorbent solvent and  treat the vials as  specified by  the referenced
   method (Table E).  Prepare a blank vial containing adsorbent and desorption
   solvent only.
5- Analyze  the desorption solutions following steps 4 through 8 used above for
   the calibration  standards.    Record  the data on the form shown  in Figure
   5-9.
6. Multiply  the average area count of the consecutive injections by the atten-
   uation factor  to  get the area value for  that sample.   NOTE:   Attenuation
   factors  which  affect the plot  traced,  but not the  area count returned by
   an electronic  integrator  should  not  be multiplied by the  average  area
   count.  Observe the  effect of attenuation changes made at the console of a
   specific  electronic integrator to  determine  the  appropriate course  of
   action.
7. If the  desorption solutions  are  to  be used  to generate the calibration
   curve, then plot  the expected standard solution  concentrations on the ab-
   scissa  (x-axis)  and  corresponding area  value  on  the  ordinate  (y-axis).
   Perform a regression analysis  and  draw  the least squares line on the plot.
   NOTE:    If the desorption  efficiencies of the  selected solvent  vary  with
   concentration  for  any  of  the  organics  to  be  analyzed,  the  relationship
   between the expected standard solution concentrations and the corresponding
   area  value  will not be strictly  linear.    Evaluate the linearity  of the
   resulting plot using control  samples, and obtain the prior approval of the
   Administrator before  utilizing a  least squares  line generated  from  such
   data.
   Calculate the  desorption efficiency  (DE),  in percent,  for  each  level of
   spike using  the  calibration  area  for  the corresponding standard prepared
   directly in the desorption solvent using the  following formula:
                                    A. - A_
                               DE =
                                      x 100%
Equation 5-13
  where
          As  = Average area value for desorption carried out at given concentration
               level,  area counts,
          Ad  = Average area value for desorption  carried out on blank sample,  area
               counts, and
          Ac  = Average calibration area value for the  corresponding standard level
               prepared directly in the desorption solvent, area counts.

     The desorption efficiency achieved at each level  must be greater than 50% for
the adsorption tube sampling and analytical method to be acceptable.  If adsorption
tubes have become the  only remaining sampling option, and the 50% criteria cannot

-------
                                                              Section No. 3.16.5
                                                              Date  June  30, 1988
                                                              Page  22

         Preparation of Liquid Standards and Desorption Efficiency  Samples
                                                                                o
Date:  Z/23/68   Preparer:   &•
Organic Compound ;
Compound Source:
                       Compound Purity (P) ;
                                                                      Liquid:
                                                    Compound Mole Weight  (M) :
Adsorbent Material: Ar.tivb\td C&fat*^ Batch No: _/£]

Standards in Solvent ' Mixture 1
Desorption solvent volume (Va ) , ml 4-00
Compound spike amount (V0 ) , ul 4-°P
Organic compound density (p) , ug/ul /. £2-S
Standard concentration (C ) , ug/ml /. O2-

Standards on Adsorbent Mixture 1
Adsorbent amount, g £>.&W>
Compound spike amount (V0 ) , ul 4-. 00
Organic compound density (p) , ug/ul /, G>23
Desorption solvent volume {VB ) , ml 4. r>0
Desorption time, min. 3O
Standard concentration (C9 ) , ug/ml /•{?£-

o Desorption

Mixture 2
4.00
fi.OO
A 6>Z?
3. £5"

Solvent:
Mixture
4.00
I2.>0t>
1. 6>2J
/"/»,4f

Mixture 2 Mixture 3
0-8 CO
6.00
1. 62 i
4-.OD
5O
3.2.5"

0-800
f^CfO
J . (02$
4.0D
•30
6-.4T

W,


Blank
/.teZ3
4.00
GC Operating Conditions
Injection port temperature, °C
Carrier gas flow rate, ml/min
Column temperature:
     Initial, °C
     Program rate,  °C/min
     Final, °C
                                                                                  O
                                       30
  Chromatographic  Results
  Injection time,  24-hr clock
  Distance to peak,  cm
  Chart  speed,  cm/min
  Retention time,  min
  Attenuation factor
  Standards in  desorption  solvent:
      Peak area  (Ac),  area  counts
  Standards and blank  from
    adsorbent material:
      Peak area  (As and Ab),
          area  counts
                                      Mixture 1   Mixture 2   Mixture 3  Blank
                                                                /5V 5?
                                                                47.3
                                         /D
                                                               /O
                                                     4.73
                                                     .2-
                                                                 857-

Desorption Efficiency Calculation
Desorption Efficiency (DE) , %
Mixture 1

-------
                                                              Section No. 3.16.5
                                                              Date June 30, 1988
                                                              Page 23

be  met,  then, subject  to the  prior approval  of  the Administrator,  explore more
vigorous desorption techniques such as longer desorption times, Bonification of the
vials during desorption, and/or other desorption solvents.

5.2  Audit Sample Analysis

    After analysis  of the calibration  standards,  and generation of a calibration
curve,  conduct  the analysis  of the  audit cylinder(s).   Audit. samples  should be
introduced into the GC by the same procedure used for the calibration standards. If
possible, the audit sample  should  be introduced into the probe for the direct and
dilution interface techniques.  The  audit  sample analysis  must agree within 10% of
the actual concentration of the audit sample before  sample analysis can begin.  If
the audit  criteria is not  met,  first try  recalibrating the GC with  the existing
standards,  and  then  reanalyze  the  audit  sample(s).   If  the 10%  criteria  still
cannot be met,  remake the standards, recalibrate  the GC, and  reanalyze the  audit
sample until  the  criteria is  met or a representative of the Administrator decides
differently.

5.3  Sample Analysis

    After the GC  has  been calibrated and  the  analysis  of the  audit sample(s) has
been conducted successfully, the samples can be analyzed.   Use the  same procedures
for sample  analysis  that were used  to  analyze the calibration standards.   Record
the GC conditions and the analytical data  on the form provided in Figure 5«1.  The
following subse'ctions  describe the  procedures for  analyzing Tedlai*  bag samples,
direct and dilution interface samples,  adsorption  tube  samples, and heated syringe
samples.

5.3-1  Analysis of Bag Samples - The following procedures are to be  used to analyze
emission samples collected in Tedlar bags  using a  GC calibrated with gaseous  cali-
bration standards  prepared  following one  or more of  the procedures  described in
Subsection 5-1-
    1.  Attach a  quick connect, or  similar connecting  device that is  compatible
        with the connection on the Tedlar bag  to the gas sampling valve on the GC.
        Attach A manometer connected to a tee on the outlet of the sample loop.
    2.  With the gas sampling valve  in the load position, attach the  first Tedlar
        bag sample to the valve.  Use a pump on the  outlet side of  the sample loop
        to flush the sample through the loop at 100 cc/min for 30  seconds.
    3.  Turn off  the  pump,  allow  the  sample loop to return to the same pressure
        used during calibration standard analysis,  and immediately switch the valve
        to the inject position.
    4.  Note the time of  the  injection on the  strip chart  recorder and/or actuate
        the electronic  integrator.   Also,  record the  sample identity,  detector
        attenuation factor, chart  speed,  sample loop temperature,  column tempera-
        ture and identity,  and  the carrier gas type  and flow rate on a data form
        such as Figure  5-1-   It is  also  recommended that the  game information be
        recorded directly on the chromatogram.   Record the operating parameters for
        the particular detector being used.
    5.  Examine  the  chromatogram  to  ensure  that  adequate resolution  is  being
        achieved for the major components  of the sample.   If adequate resolution is
        not being achieved, vary the GC conditions  until resolution  is  achieved,
        and reanalyze  the standards to recalibrate  the GC at the new conditions.
    6.  After conducting  the  analysis with  acceptable  peak  resolution,  determine
        the retention time of the sample components and  compare them to  the reten-

-------
                                                              Section No.  3-16.5
                                                              Date June 30, 1988
                                                              Page 24

        tion times for  the  standard compounds.   To qualitatively identify an indi-
        vidual sample  component  as a target  compound,  the retention  time for the
        component must match within 0.5 seconds or 1%, whichever is greater, of the
        retention  time of  the  target  compound  determined  with the  calibration
        standards.
     7. Repeat the  injection of  the  first sample until the  area count  for  each
        identified target compound from two consecutive injections give area counts
        within 5 percent of their average.
     8. Multiply the average area count of the consecutive injections by the atten-
        uation factor  to  get the area value  for that sample, and record the  area
        value  on the  data  form  provided in  Figure  5.1.   NOTE: When  dispensing
        liquid from  a  syringe,   take  care to account  for the  volume  of liquid
        present  in the  syringe needle.   In general,  the potential error resulting
        from  the volume  of the  needle  is most  conveniently avoided by ensuring
        that  the needle  volume  is  completely  full  of liquid  upon -filling the
        syringe and dispensing from it.   If air  pockets  exist in the syringe after
        filling,  this will be almost impossible.
     9. Repeat the procedure for the other two samples collected at the same sampl-
        ing location.
    10. Immediately following the analysis of the last sample,  reanalyze the cali-
        bration  standards,  and  compare the  area values  for  each standard  to the
        corresponding  area  values from  the  first calibration  analysis.    If the
        individual area values  are within 5% of their mean  value,  use  the  mean
        values to  generate  a final  calibration  curve for determining the sample
        concentrations.   If the  individual values are not within  5#  of  their  mean
        values, generate a calibration curve using the results of the second analy-
        sis of the calibration standards,  and report the  sample results compared to
        both standard curves.
    Determine  the  bag sample water content by  measuring the temperature  and the
barometric pressure near the bag. Use  water saturation vapor pressure chart, assum-
ing the relative humidity of the bag  to be 100% unless  a lower  value is  known, to
determine the  water  vapor content as  a decimal figure (% divided  by  100).   If the
bag has been heated  during  sampling,  the flue gas or duct  moisture  content should
be determined using Method 4.

5-3«2   Analysis of  Direct   Interface  Samples -  Prior   to  analysis  of the direct
interface sample,  the  GC should be  calibrated  using a set  of  gaseous  standards
prepared by  one  of  the techniques described in  Subsection  5-1 and  a  successful
analysis of an audit sample should be  completed.   If possible,  the  audit samples
should be  introduced directly into the probe.   Otherwise,  the audit samples are
introduced into  the  sample  line  immediately  following the probe.   The calibration
is done by disconnecting the sample line coming from the  probe, from the gas sampl-
ing valve sample loop  inlet, and connecting  the  calibration standards  to the  loop
for analysis.    During the  analysis  of  the  calibration standards  and  the audit
sample(s),  make  certain  that  the sample  loop pressure  immediately  prior  to the
injection of  the standards  is at the same pressure  that will be used  for sample
analysis.  To  analyze the  direct  interface  samples after GC calibration,  use the
following procedures:
     1. Reconnect the sample line to  the  inlet of the gas sample  loop,  switch the
        valve  to the  load  position,  and turn  on the  sampling pump. Adjust the
        sampling rate  to  at least 100 cc/minute, and, for the  first  sample, purge
        the sample  line long enough  to  flush the sample  loop and  the  preceding
        volume of tubing a minimum of  7 times.
o
o
o

-------
                                                              Section No. 3.16.5
                                                              Date June 30, 1988
                                                              Page 25

      2.  After purging the sampling system and the sample loop, decrease the sample
         flow using the needle valve downstream of  the  loop  until  the loop pressure,
         measured by a water manometer connected to a tee at the  outlet of loop, is
         equal to the pressure used during calibration.
      3.  Once the  loop  is at  the  correct pressure, immediately  switch  the sample
         valve to the inject position.  Note the time of the injection on the strip
         chart recorder and/or actuate the electronic integrator.  The flow through
         the  sample line can  be  returned  to lOOcc/min after sample injection, and,
         after the unretained  compounds are detected,  the  gas  sample  valve can be
         switched back  to the load position.    The system will then be  ready to
         inject  the second sample as soon  as the  first  analysis  is completed.
      4.  Record   the  sample  identity, detector  attenuation  factor,  chart speed,
         sample  loop temperature,  column  temperature  and identity,  and the carrier
         gas  type and flow  rate  on a form  such  as Figure  5-1 •.  It  is also recom-
         mended  that the same information be recorded directly  on the chromatogram.
         Record  the operating parameters for the  particular  detector being used.
      5.  Examine the  chromatogram  to ensure  that  adequate  resolution  is  being
         achieved for the  major components of the sample.  If adequate resolution is
         not  being achieved,  vary  the GC  conditions until  resolution is achieved,
         and  reanalyze the  standards to recalibrate  the GC at the  new conditions.
      6.  Immediately after the first analysis is comple.te,  repeat steps  2 and 3 to
         begin the  analysis  of the  second  sample.
      7.  After conducting  the analysis of the  first  sample with  acceptable peak
         resolution,  determine  the  retention  time  of  the sample  components  and
         compare them to the retention times for the standard compounds.  To quali-
         tatively identify an individual  sample component as a  target compound, the
         retention  time for  the  component  must  match,  within  0.5  seconds  or 1%,
         whichever  is  greater,  the  retention time of the target compound determined
         with  the calibration  standards.
      8.  At the  completion of  the  analysis of the second sample, determine if the
         area  counts for the  two consecutive injections give area  counts within 5
        percent  of their  average.   If   this  criterion  cannot  be  met due  to  the
         length  of  the analysis,  and  the  emissions are known to  vary  because of a
        cyclic  or  batch process, then the  analysis results can still  be used with
        the prior approval of  the Administrator.
     9. Analyze a minimum of three  samples collected by direct  interface to consti-
        tute an emissions test.
    10. Immediately following  the  analysis of  the  last sample,  reanalyze the cali-
        bration  standards,  and  compare the area values  for each standard  to  the
        corresponding .area values  frpm   the .first .calibration analysis.   If  the
        individual  area values  are within  5% of  their mean  value.,, ,use  the  mean
        values  to  generate a final calibration  curve  to  determine the  sample
        concentrations.   If the  individual values  are not  within 5%  of  their mean
        values,  generate a calibration curve using the results of the second analy-
        sis of the calibration standards,  and report the sample results compared to
        both standard curves.

5.3.3  Analysis of Dilution Interface Samples - For the analysis of dilution inter-
face samples, the procedures  described for direct  interface sampling in Subsection
5-3-2 should  be followed,  with  the  addition  of a check  of the dilution  system.

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                                                              Section No.  3.16.5
                                                              Date June 30,  1988
                                                              Page 26

Prior  to  any sample  analysis,  the GC  must first be  calibrated,  followed by the
dilution system check and an analysis of  the audit sample(s).   The audit  sample(s)
are introduced preferably  into the inlet  to the  dilution system or  directly  into
the gas sampling valve.  Use the following procedures to conduct  the check of the
dilution system:
     1. Heat the dilution  system to the  desired  temperature (0° to  3°C  above the
        source temperature) or, if  the  dilution system components  can not tolerate
        that temperature, to a temperature high enough to prevent condensation.
     2. Adjust the dilution system to achieve the  desired dilution rate, and intro-
        duce a high concentration target gas into  the inlet of the dilution system.
        After dilution  through the stage(s)  to  be  used  for  actual  samples, the
        target gas  should  be  at a concentration that  is  within  the calibration
        range.
     3. Purge the gas sample loop with  diluted high concentration  target gas  at a
        rate of 100  cc/min for 1 minute, adjust the  loop pressure  measured by a
        water manometer connected to a  tee at  the outlet of the loop,  to the  loop
        pressure  that was  used during  calibration and will be  used  during sample
        analysis.   The procedure  for pressure  adjustment for the  sample  loop  will
        vary with the type of  dilution  system  that is used.  In general,  the  loop
        pressure  can be  lowered  by reducing the  flow  into the  loop  and  raised  by
        restricting the  flow from the loop.
     4. After achieving  the proper loop  pressure,  immediately switch the gas sample
        valve to  the  inject position.
     5. Note the  time of the injection  on the strip chart  recorder and/or  actuate
        the electronic  integrator.    Also, record  the  sample   identity,  detector
        attenuation factor, chart speed,  sample loop  temperature,  column tempera-
        ture and  identity,  and  the carrier gas  type and flow rate on a form such  as
        Figure  5.1 •  It  is  also  recommended that  the  same  information be recorded
        directly  on  the chromatogram.    Record  the  operating  parameters  for the
        particular detector being used.
     6. Determine  the peak  area and retention time for the target compound used for
        the dilution  check,  and calculate the area value  using the detector attenu-
        ation.   Compare  the retention  time to the  retention  time of the target
        compound  calibration standard.   The retention times should agree within 0.5
        seconds or 1%,  whichever is greater.  If  the retention  times  do not agree,
        identify  the  problem and  repeat  the dilution  check.
     7. Calculate  the concentration of  the dilution  check gas  (Cd) using the  fol-
        lowing  formula.
                                                                      Equation 5-14
                   S
     where

             Y =  Dilution check target compound peak area,  area counts,
             b =  y-intercept of the calibration curve,  area counts,
             S =  Slope of the calibration curve,  area counts/ppmv ,  and              /"""N
             d =  Dilution rate of the dilution system,  dimensionless.                f   J

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                                                              Section No. 3.16.5
                                                              Date June 30, 1988
                                                              Page 27

     8. If the calculated value for the dilution check gas is not within 10# of the
        actual dilution check gas, then determine  if  the GC or the dilution system
        is in error.  Check the calibration of the GC by analyzing one of the cali-
        bration  samples  directly  bypassing the  dilution  system.    If  the GC  is
        properly calibrated, then adjust the dilution system, and repeat the analy-
        sis of the  dilution check gas until the calculated results  are  within 1Q%
        of the actual concentration.
     Once the dilution system and  the  GC  are operating properly,  analyze the audit
sample(s).  Upon completion of  a successful audit, the  system is ready  to analyze
samples following the procedures described in Subsection 5-3-2.  To load the sample
from the dilution system  may not require a pump on the  outlet of the sample loop,
but calibration  of  the GC using standards  prepared  in Tedlar  bags  will require a
pump.  The system should be configured so that the pump can be taken off line when
it is not needed.

5-3«4  Analysis  of  Adsorption Tube Samples -  Prior  to  the analysis of  adsorption
tube samples,  the  target  compounds  adsorbed  on  the  adsorption  material  must  be
desorbed.  The procedures  found to give  acceptable desorption efficiencies deter-
mined in Subsection 5.1.k  should be  used.  The procedures  for the analysis of the
sample desorption solutions  are  the  same as those used  for the standards.  During
sample analysis, the  sample collection  efficiency must be  determined.   Use the
following procedures to determine the collection efficiency:
     1. Desorb the  primary and backup sections  of the  tubes  separately using the
        procedures  found  to give  acceptable  (50%) desorption efficiency  for the
        spiked adsorption material.  Use  the same  final volume of desorption solu-
        tion for  the samples as was used  for the standard solutions.  If more than
        one adsorption tube was used  in  series  per  test run,  delay desorbing the
        additional  tubes until  the analysis of  the  primary and  backup  section of
        the first tube is  complete,  and the  collection efficiency  for the first
        tube determined.   Select the  samples  from the sampling  run  when the  flue
        gas or duct moisture was the  highest  and, if known,  when the target  com-
        pound concentrations were the highest and analyze them first.
     2. Calibrate the GC using standards  prepared directly in desorption  solvent or
        prepared on adsorbent and desorbed.
     3. Select a suitably  sized  injection syringe  (5~ or  10-wl),  and  flush the
        syringe with acetone (or some other suitable  solvent if acetone is a target
        compound) to clean the syringe.
     4. Flush the syringe  with the  desorption solution  from  the   tube's  backup
        section by withdrawing a syringe  full of the  solution from the septum vial,
        and dispensing the solution into  a beaker containing charcoal adsorbent.
     5- Refill the  syringe with the backup section  desorption solution,  withdraw
        the syringe  from  the vial, and wipe the syringe needle  with a  laboratory
        tissue.
     6. Adjust the  syringe  volume  down to the amount used  for injecting standards
        and inject  the sample into the GC.   Note  the time  of  the injection on the
        strip chart recorder  and/or  actuate  the electronic  integrator.   Also,
        record the   sample  identity,  detector  attenuation factor,  chart  speed,
        injection port temperature, column temperature and identity,  and  the carri-
        er gas type  and flow rate on  the  data form shown in Figure 5•1•  It is  also
        recommended  that  the same information be recorded directly on the chromato-

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                                                          Section No. 3.16.5
                                                          Date June 30, 1988
                                                          Page 28

    gram.   Record the operating  parameters for the  particular  detector being
    used.
 7. After  the  analysis,  determine  the  retention time  of  the major  sample
    components, and compare these retention times to the retention times deter-
    mined for the target compounds during analysis of the standards.  To quali-
    tatively identify an individual  sample  component  as a target compound, the
    retention  time  for  the  component must match, within  0.5 seconds  or 1%,
    whichever is  greater,  the  retention  time of the target compound determined
    with  the  calibration standards.    Determine the peak area for  each target
    compound identified in the sample.
 8. Repeat  the  injection of the  first sample  until  the area counts  for each
    identified  target  compound from two consecutive  injections are  within 5
    percent of their average.
 9. Multiply the average area count of the consecutive injections by the atten-
    uation factor to get the area value for that sample.
10. Next  analyze  the desorption solution from  the  primary  section  of the same
    adsorption tube following steps 4 through 9 above.
11. For each target compound, calculate the total weight (W), in ug, present in
    each  section,  taking  into  account  the desorption  efficiency using the
    formula below.

                      (Y - b)    1
         W  or Wb  =  	 x —                                Equation 5-15
                         S      DE

 where

         Y = Average value for the target compound in  the  section  (primary or
             backup), area counts,
         b = y-intercept from  the  three-point  calibration  curve  for the target
             compound,  area counts,
         S = Slope from the three-point calibration curve for the target
             compound,  area/ug, and
        DE = Desorption efficiency (if standards prepared directly in
             desorption solvent are used for calibration).

12. Determine the percent  of the  total catch found in  the  primary  section for
    each target compound identified using the following formula.
                   mpx
         Ecx =	x 100#                                  Equation 5-16
               Kx + m*x)

where
         ECJ£ = Collection efficiency of the primary section for target compound
               x, percent,
         mpx = Catch of compound x in the primary section, ug, and
         mhx = Catch of compound x in the backup section, ug.
o
o
                                                                                       o

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                                                              Section No. 3.16.5
                                                              Date June 30, 1988
                             ,                                 Page 29

        If  the  collection efficiency for the primary section  for each target com-
        pound identified  is >^ 90%, then the collection efficiency for that compound
        is  acceptable.   If the collection efficiency for  all  the target compounds
        identified in the sample is acceptable, then the analysis of any additional
        tubes used in series behind  the  first  tube will not be necessary.  Proceed
        with the analysis of the other adsorption tube samples.
    12. If  the  collection  efficiency for  any identified  target compound  is  not
        acceptable, then  analyze  the  second  tube  (if used)  connected in series and
        determine the collection efficiency for that tube using the steps described
        above.   If the  second  tube does not  exhibit acceptable collection and a
        third tube  was  used,  analyze the  third tube.   If acceptable collection
        efficiency cannot be demonstrated for the sampling system,  then the emis-
        sion test using adsorption tubes will not be acceptable.
    13. Immediately following the analysis of  the last  sample, reanalyze the cali-
        bration standards,  and compare  the  area values  for  each standard  to the
        corresponding area  values  from  the  first calibration  analysis.    If the
        individual area  values are  within 5%  of their mean  value, use  the mean
        values  to  generate a  final  calibration  curve  for determining  the  sample
        concentrations.    If  the individual values are not within 5% of their mean
        values,  generate  a calibration curve using the results of the second analy-
        sis of the calibration standards, and report the sample results compared to
        both standard curves.

5.3-5  Analysts of Heated Syringe Gas Samples  by Direct Injection - For the analy-
sis of samples  collected in heated syringes, the GC will  have to be equipped with
an injection septum fitted to the gas sampling valve sample loop inlet.  Calibrate
the GC  following one of the procedures described  in  Subsection 5.1  for gaseous
calibration standards.   Analyze the heated  syringe samples by  the following proce-
dures :
     1. Attach a GC septum  to  a quick connect, or  equivalent, compatible with the
        connector on the gas sampling valve, and attach this  connector to the gas
        sampling valve.
     2. Insert the needle of the  heated syringe  through the septum,  and purge the
        sample loop by  injecting a  volume of  the gas  sample at least  ten times
        greater than the  sample loop volume.
     3. Allow the sample  loop pressure,  measured  by a water manometer connected to
        a tee on  the  outlet of  the sample loop,  to reach the  same loop pressure
        seen during analysis of the calibration  standards,  and immediately switch
        the gas  sample valve to the inject position.
     4. Note the time of the injection on the strip  chart recorder and/or actuate
        the electronic  integrator.    Also,  record  the  sample  identity,  detector
        attenuation factor,  chart speed,  sample loop temperature and volume,  column
        temperature and identity,  and the carrier gas type and flow rate on a form
        such as Figure 5-1-   It is  also recommended that the same  information be
        recorded directly on the chromatogram.   Record the operating parameters for
        the particular detector being used.
     5.  Examine   the  chromatogram  to  ensure  that  adequate   resolution  is  being
        achieved for the  major  components of the sample.  If adequate resolution is
        not being achieved,  vary  the GC  conditions until resolution  is  achieved,
        and reanalyze  the standards  to recalibrate the GC at the new conditions.

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                                                          Section No. 3.16.5         x—v
                                                          Date June 30, 1988        (   )
                                                          Page 30                   ^*~*/

 6. After  conducting  the analysis  with acceptable peak  resolution,  determine
    the retention time of the  sample  components  and compare them to the reten-
    tion times for  the standard  compounds.   To qualitatively identify an indi-
    vidual sample component as a  target  compound,  the retention  tine for the
    component must  match, within 0.5 seconds or 1%,  whichever is greater, the
    retention  time  of  the  target compound  determined  with  the  calibration
    standards.
 7. Repeat the  injection of the  first sample until  the area  counts  for each
    identified target  compound from  two consecutive  injections are  within  5
    percent of their average.
 8. Multiply the average area count of the consecutive injections by the atten-
    uation factor to get the area value for that sample.
 9. Repeat the procedure for the other two samples collected at the same sampl-
    ing location.
10. Immediately following the  analysis  of  the  last  sample,  reanalyze the cali-
    bration standards, and  compare the area values  for  each  standard  to the
    corresponding area  values from the  first  calibration  analysis.    If the
    individual area values  are  within 5%  of  their mean  value, use  the mean
    values to  generate  a final  calibration curve  for determining  the  sample
    concentrations.   If  the individual values  are not within  5% of their mean
    values, generate a calibration curve using the results of the second analy-
    sis of the calibration standards,  and report the sample results compared to
    both standard curves.
o
                                                                                    o

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                                                              Section No.  3.16.5
                                                              Date June 30,  1988
                                                              Page 31
Date	 Plant Name 	 Sampling Location 	

Checks for Analysis of All Calibration Standards

    A minimum of three concentration levels used for each target compound?
        	 yes 	 no.  (The concentration used should bracket the expected
        concentrations of the actual field samples.)

    Proper GC conditions established prior to standard analysis? 	 yes 	 no.
        (For  initial  conditions use analytical  conditions found to  be acceptable
        during preliminary survey sample analysis.)

    Individual peak  areas  for consecutive injections  within 5% of  their mean for
        each  target  compound? 	 yes 	  no.    (Repeat analysis  of standards
        until 5% criteria is met.)

    Second analysis of standards after sample analysis completed? 	 yes 	 no.

    Peak areas for repeat analysis of each standard within 5% of their mean peak
        area? 	 yes 	no.  (If no, then report sample results compared to both
        standard curves.)

Checks for Calibrations using Commercial Cylinder Gases

    Vendor concentration verified by direct analysis? 	 yes	 no.

    Sample loop purged for 30 seconds  at 100 ml/min prior to injection of calibra-
        tion standards? 	 yes 	 no.

Checks for Preparation and Use of Calibration Standards Prepared by Dilution

    Dilution system flowmeters calibrated? 	 yes 	 no.  (Calibrate following
        procedure described in Subsection 2.1.3.)

    Sample loop purged for 30 seconds  at 100 ml/min prior to injection of calibra-
        tion standards? 	 yes 	 no.

    Dilution ratio for  dilution system verified? 	 yes 	 no.   (Analysis of
        low concentration cylinder gas after establishing calibration curve
        recommended to  verify dilution procedure,  but not  required  since  audit
        sample will also verify dilution ratio.)


           Figure 5-10.   Postsampling operations  checklist.

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                                                              Section No.  3.16.5
                                                              Date June 30,  1988       x—v
                                                              Page 32                  (J

Figure 5.10 (Continued)

Checks  for  Preparation and  Use of  Calibration Standards by Direct  Injection  of
Gaseous Compounds or Liquid Injection

    Tedlar bag used to contain prepared standard leak and contamination free?
        yes 	 no 	.

    Dry gas meter used to  fill  bag calibrated?  	 yes  	 no.   (Calibrate meter
        following procedure described in Subsection 2.1.2.)

    Organic standard material used for injection 99-9# pure?  	 yes 	 no.  (If
        no, then determine purity and use to correct calculated calibration
        standard concentration.)

    Prepared standard allowed to equilibrate prior to injection? 	 yes 	 no.
        (Massage bag by alternately depressing opposite ends  50 times.)

    Sample loop purged for 30 seconds  at  100  ml/min prior to injection of calibra-
        tion standards? 	 yes 	 no.


Development of Relative Response Factors and Retention Times

    Suitable target organic or surrogate compound selected? 	 yes 	 no.          I   J
        (Select compound that  is stable,  easy  to  prepare in the field,  and has a
        retention time similar to the target organic compounds.)

    Relative response factors and retention times  verified in the laboratory prior
        to actual field use? 	 yes 	 no.  (If no, verify following the
        procedure described in Subsection 5.1.4.)


Checks for Preparation. Use, and Determination of Desorption  Efficiency for Adsorp-
tion Tube Standards

    Organic standard material used for injection 99.9# pure?  	 yes 	 no.  (If
        no, then determine purity and use to correct calculated calibration
        standard concentration.)

    Correct adsorbent material  and desorption solvent selected? 	  yes 	 no.
        (Refer to Table B in Method Highlights Section for proper adsorbent
        material and desorption solvent.)

    Desorption efficiency determined for adsorbent to be used for field sampling?
             yes 	 no.   (If no, follow the procedure described in Subsection
        5.1.5.)
                                                                                       O

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                                                              Section No. 3.16.5
                                                              Date June 30, 1988
                                                              Page 33
Figure 5.10   (Continued)

Checks for All GC Analysis of Field Samples

    Check type of carrier gas used: helium 	, nitrogen 	, other
    Carrier gas flow rate and pressure set correctly?  	 yes 	 no. (Carrier
        gas flow rate and pressure set according to conditions developed during
        presurvey  sample analysis and  within limitations of the GC  as specified
        by GC manufacturer.)

    Oxygen and hydrogen  flow rate and pressure for FID correct? 	 yes 	 no
        (Oxygen and hydrogen gas flow rate and pressure for FID set according to
        conditions developed during presurvey sample analysis and within
        limitations of the GC as specified by GC manufacturer.)

    Individual peak  areas for consecutive injections  within 5% of  their  mean for
        each  target  compound? 	  yes 	 no.    (Repeat  analysis  of standards
        until 5# criteria is met.)

    Audit sample analyzed and results within 10% of actual value? 	 yes 	 no.
        (If no, recalibrate GC and/or reanalyze audit sample.)

Checks Type of Standard Used for Tedlar Bag Sample Analysis

    Gas cylinders 	, dilution of gas cylinders 	, direct gas injection 	,
        direct liquid injection 	, and/or relative response factors and
        retention times 	.

Checks For GC Analysis Of Tedlar Bag Samples

    Sample loop purged for 30 sec. at  100  ml/min prior to injection of calibration
        standards? 	 yes 	 no.

    Stability of gas sample  in Tedlar bag determined? 	 yes 	 no.    (Deter-
        mine stability by conducting a second analysis  after the first at  a time
        period equal to  the time between  collection  and the first  analysis.   The
        change in  concentration  between the  first and  second analysis should  be
        less than 10%.)

    Retention of target compounds in Tedlar bag  determined? 	  yes 	  no.   (If
        no,  then follow the procedure described in  Subsection 5-3-1-)

Check GC Interface Technique Used

    Direct Interface    ,  10:1 Dilution Interface    ,  100:1 Dilution Interface

-------
                                                              Section No. 3.16.5
                                                              Date June 30,  1988
                                                              Page 34

Figure 5.10 (Continued)

Checks For Suitability of GC Interface Technique

    Analytical interference due to moisture content of source gas? _ yes  _ no.
        (Moisture in the source gas must not  interfere with  analysis in regard
       to peak resolution according to EPA Method 625 criterion where the
        baseline-to-valley height between adjacent peaks  ic less than 2$% of the
        sum of the two adjacent peaks.)

    Physical requirements for equipment met on-site?  _ yes _ no.  (The
        physical requirements for the equipment include sheltered environment,
        "clean", uninterrupted power source suited  for equipment,  and adherence to
        safety aspects related to explosion risk areas.)

    Source gas concentration below level of GC  detector  saturation? _ yes  _ no.
        (Concentrations delivered to  the  detector can be reduced  by using  smaller
        gas sample loops and/or dilution interface . )

    Sampling systems purged with 7 changes of system volume prior to sample
        analysis? _ yes _ no.

Check Type(s) of Standards Used for Interface Techniques

    Gas cylinders _ , dilution of gas cylinders _ ,  direct gas injection _ ,
        direct liquid injection _ , and/or relative response factors and
        retention times _ .

Checks For Dilution Interface Analytical Apparatus

    Dilution  rate verified  (within  10%)  by introducing high concentration  gas
        through dilution system and analyzing diluted gas? _ yes _ no.
        (If  dilution  rate  not verified,  then first  check  calibration of  GC  by
        reanalyzing a calibration standard and  then adjust dilution system  to give
        desired ratio) .

    Sampling systems purged with 7 changes of system volume prior to sample
        analysis? _ yes _ no.

Check Type of Standard Used for Adsorption Tube Analysis

    Prepared directly in desorption solvent _ , and/or prepared  on adsorbent and
        desorbed _ .

Checks for GC Analysis of Adsorption Tube Samples

    Desorption procedure used identical to procedure used to  determine the
        desorption efficiency? _ yes _ no.
S~\
o
 o

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                                                              Section No. 3.16.5
                                                              Date June 30, 1988
                                                              Page 35
Figure 5-10  (Continued)
    Collection  efficiency  determined for  adsorption tubes  used for  actual  field
        sampling? 	 yes  	 no.   (If no,  then  determine collection efficiency
        following the procedures described in Subsection 5-3-4.)

Check Type of Standard Used for Analysis of Heated Syringe Samples

    Gas cylinders 	,  dilution of gas cylinders 	,  direct gas injection 	,
        direct liquid injection 	, and/or relative response factors and
        retention times
                                           XT/ -•

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                                                              Section No. 3-16.5
                                                              Date June 30, 1988
                                                              Page 36
                  Table 5.1.  ACTIVITY MATRIX FOR SAMPLE ANALYSIS
Characteristic
Calibration
Standards
All calibrations
Commercial gas
cylinder mixtures
Gas standards from
high concentration
gas cylinders
Standards prepared
by direct gas
injection
Standards prepared
by liquid
injection
(Continued)
 Acceptance limits
1) Standard analysis
performed under same
GC conditions to be
used for samples

2) Three-point
(minimum) calibra-
tion curve generated
for each target
compound

3) Sufficient amount
of each standard to
recalibrate after
samples are analyzed
Certified by direct
analysis (within 5#
of manufacturer's
value); three levels
bracketing samples
Dilution ratio of
dilution system
verified (optional)
with calculated val-
ue using calibration
curve within 10%
of actual cone.
Gas injected 99.9#
pure, or calculated
standard concentra-
tion corrected for
gas impurity
Liquid injected
99-92 Pure, or
calculated standard
corrected for
liquid impurity
Frequency and method
   of measurement
Before analysis of
calibration standards
determine sample ana-
lysis conditions

Before analysis ac-
quire or prepare stan-
dards for each target
compound at three
levels

Prior to initial
calibration and sample
analysis, determine
amount needed
Prior to use, check if
independent analysis
conducted and accept-
able and standards
will bracket samples
Prior to sample analy-
sis; calibration curve
from standards verif-
ied by analysis of an
undiluted sample
When calculating stan-
dard concentration,
determine purity of
gas standard
When calculating stan-
dard concentration,
determine purity of
liquid standard
Action if
requirements
are not met
Reanalyze stan-
dards under con-
ditions to be
used for samples

Acquire or pre-
pare standards at
at three levels
to bracket
samples

Acquire or
prepare
enough
standards
Procure certified
gas cylinders in
proper range
Identify and
correct problems
with dilution
system, and
remake, reana-
lyze, and re-
verify standards
Use pure gas or
determine purity
Use pure liquid
or determine
purity
                                                                   o
                                                                                       o
                      o

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Table 5.1   (Continued)
                                                              Section No. 3.16.5
                                                              Date June 30, 1988
                                                              Page 37
Characteristic
Calibration
Standards

Relative response
factors and rela-
tive retention
times
Standards prepared
for adsorption
tube samples
Audit sample
analysis
Sample Analysis

All samples
 Acceptance limits
Proper target or
surrogate standard
selected for on-site
calibration; method
verified (calculated
results within 10%
of actual concentra-
tion)
1) Liquid injected
99.9% pure, or
calculated standard
corrected for

2) Acceptable
desorption effici-
ency for target com-
pounds on adsorbent
material (>50#)
Analytical result
for audit sample
within 10% of actual
concentration
1) Audit sample
analysis within 10%
of actual cone.

2) Sample analysis
conditions the same
as conditions used
for analysis of
standards
Frequency and method
   of measurement
When selecting stan-
dard choose stable,
easy to prepare stan-
dard with retention
time near or between
target compounds; ver-
fied following proced-
ures described in
Subsection 5.1.5
When calculating stan-
dard concentration,
determine purity of
liquid standard

During calibration
standard analysis
determine desorption
efficiency for each
target compound (see
Subsection 5.1.5)
After initial cali-
bration and prior to
sample analysis, ana-
lyze audit sample
Prior to sample ana-
lysis, analyze audit
sample

Prior to sample ana-
lysis check that ana-
lytical conditions are
the same as those used
for standard analysis
Action if
requirements
are not met
Select different
target or
surrogate
compound; if
procedure cannot
be verified
use calibration
standard for each
target compound
Use pure liquid
or determine
purity
                                                                  Try longer de-
                                                                  sorption times,
                                                                  more vigorous
                                                                  desorption condi-
                                                                  tions ,  and/or
                                                                  other desorbents
Reanalyze audit
sample, if not
acceptable, re-
make and reana-
lyze standards
Analyze audit
sample
                                                                  Establish the
                                                                  same analytical
                                                                  conditions used
                                                                  during analysis
                                                                  of standards
(Continued)

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Table 5.1  (Continued)
                                                              Section No. 3-16.5
                                                              Date June 30, 1988
                                                              Page 38
                                                                   o
Characteris tic
Sample Analysis

All samples
Bag samples
 Acceptance limits
3) Retention times
for target compounds
identified in sample
within 0.5 seconds
or 1% of standards
                    4) Area counts for
                    consecutive injec-
                    tions of samples
                    within 5# of their
                    average for each
                    target compound
                    identified in sample
                    5) All three samples
                    constituting a test
                    analyzed together

                    6) After sample ana-
                    lysis, repeat analy-
                    sis of standards;
                    area counts for each
                    standard analysis
                    within 5% of their
                    mean
1) Bag sample moist-
ure content deter-
mined
                    2) Stability check
                    conducted on bag
                    content (<1Q% change
                    between first and
                    second analysis)
Frequency and method
   of measurement
After analysis, deter-
mine retention times
for major components
in sample and compare
to standard retention
times

After second analysis
of a sample, calculate
average area for first
and second analysis
and percent difference
of single analysis
from the average
                      During sample analysis
                      After analysis of last
                      sample repeat standard
                      analysis;  calculate
                      mean area counts and
                      percent difference for
                      each standard
During analysis using
vapor pressure chart
assuming 100% or known
value for relative
humidity

Second analysis con-
ducted n days after
first analysis where
n equals the number of
days between sample
collection and first
analysis
Action if
requirements
are not met
Qualitative
identification
requires reten-
times within 0.5
seconds or 1%;
repeat analysis

Repeat sample
injections until
consecutive in-
jections are
achieved meeting
the 5X criteria
for each target
compound

Analyze remaining
samples
                        Report sample
                        results using
                        both curves, if
                        5# criteria not
                        met
                                                                                       O
Measure ambient
pressure and
temperature near
bag
                                              Conduct stabil-
                                              ity check and if
                                              criteria not met
                                              then correct sam-
                                              ple results with
                                              approval of
                                              Administrator
                                                                                        o
(Continued)
                                                   '

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                                                              Section No. 3.16.5
                                                              Date June 30, 1988
                                                              Page 39
Table 5.1  (Continued)
Characteristic
Sample Analysis

Direct interface
samples
Dilution interface
samples
Adsorption tube
samples
 Acceptance limits
Two consecutive
injections give
area counts within
5# of their mean
1) Dilution ratio
verified (results
from analysis of
high concentration
standard through
dilution system
within 10% of actual
concentration

2) Two consecutive
injections give
area counts within
5% of their mean
Collection effici-
ency determined for
adsorption tubes
(902 of each target
compound identified
caught on primary
section)
Frequency and method
   of measurement
After second analysis,
calculate average area
counts and percent
difference
Prior to sample ana-
lysis analyze high
concentration gas
introduced through
dilution system
                                          After second analysis,
                                          calculate average area
                                          counts and percent
                                          difference
Desorb and analyze
primary and backup
sections separately
Action if
requirements
are not met
Due to cyclic or
batch processes
and analysis
time, emission
levels may vary;
use results with
the prior appro-
val of the Ad-
ministrator
Identify problem;
recalibrate GC or
adjust dilution
system and repeat
analysis of high
concentration
gas
                        Due to cyclic or
                        batch processes
                        and analysis
                        time, emission
                        levels may vary;
                        use results with
                        the prior ap-
                        proval of the
                        Administrator
Analyze addi-
tional tube(s) if
used as backups
to first tube; if
criteria cannot
be met, test is
not valid

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o
o
o

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                                                                 Section No. 3.16.6
                                                                 Date June 30, 1988
                                                                 Page 1
6.0   CALCULATIONS

      Calculation  errors  due  to procedural or mathematical mistakes can be a part of
 total system error.   Therefore,  it is recommended that each set of calculations be
 repeated or spotchecked, preferably by  a  team member other than  the  one who per-
 formed the original calculations.  If a difference greater than typical round-off
 error is detected,  the calculations should be checked step-by-step until the source
 of error is found  and corrected.   A computer program  is  advantageous in reducing
 calculation errors.   If  a standardized computer program is used, the original data
 entered  should be included in the printout so it can be reviewed;  if differences
 are observed,  a  new  computer run should be  made.  Table  6.1 at the end  of this
 section  summarizes  the quality assurance activities for calculations.
      Calculations should be  carried out to at least one extra decimal figure beyond
 that  of  the acquired  data and should  be  rounded off after final calculation to two
 significant digits for  each run  or  sample.   All rounding  of numbers  should be
 performed in accordance  with the ASTM 380-?6  procedures.   All calculations should
 then  be  recorded  on a calculation form such as the ones in Figures 6.1 and 6.2 for
 analysis by gas or liquid injection, respectively.

 6.1  Calculations for GC Analysis Using Gas Injection

      The same  equation can be used to calculate  the  concentration of each organic
 in Method 18 samples  whenever the sampling technique used  yields  a gaseous sample
 which can be injected into the GC.  These  techniques  are:   (1) the integrated bag
 sampling technique,  (2)  the  heated bag  sampling technique,  (3)  the prefilled bag
 sampling technique, (4)  the  direct interface  sampling technique, and (5) the dilu-
 tion  interface sampling  technique.   This equation  is used  to calculate  the sample
 concentration  (Cc) in ppm on  a dry basis as follows:
                         Fr K
                                                                       Equation 6-1
              Pi Tr
where
     B..
     K
Concentration of organic from calibration curve, ppm,
Reference pressure, the barometric pressure or absolute sample loop
pressure recorded during calibration, mm Hg,
Sample loop temperature at time of sample analysis, °K,
Barometric or absolute sample loop pressure at time of sample analysis,
mm Hg,
Reference temperature, the temperature of the sample loop recorded
during calibration, °K,
Water vapor content of the stack gas, proportion by volume,
Relative response factor, if applicable (see Subsection 5-I-5).  and
Dilution factor (applicable only for dilution interface and  prefilled
bag sampling; for a 10 to 1 dilution, K = 10).

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                                                                 Section No. 3.16.6
                                                                 Date June 30, 1988
                                                                 Page 2
6.2  Calculations for GC Analysis by Liquid Injection
     For Method  18,  liquid injection GC analyses are used  in conjunction with the
adsorption tube  sampling procedure.   The same general  equations are typically used
to calculate the concentration of  each  organic in a sample collected on an adsorp-
tion tube.   However, the  tester is  referred to  the National Institute of Occupa-
tional  Health  and  Safety   (NIOSH) method  (see  Table  B  in the  Method Highlights
Section) for specifics on  calculations  for particular  organics.  The general equa-
tions are shown below.

6.2.1  Sample Volume Corrected to Standard Conditions on a Dry Basis - The correct-
ed sample volume (VBtd(dry) is calculated as shown.

                     T    P    v                      P    V
                     Astd  *bar vm              „ „    *b a r vm
                                               „ „
     Vltd(d    =  - : -  =  0.3858
                   P.«« T. (i -B../K)'             T.
                                                                       Equation 6-2

where

     T,td/p,td  =  °-3858 °K/mm Hg,
     Vn         =  Sample volume measured, L,
     Pbar       =  Barometric pressure during sampling, mm Hg,
     T8         =  Temperature of sample gas, °K,
     Bw$        =  Water vapor of stack gas, proportion by volume, and
     K          =  Dilution factor, if applicable.

"Note:  Only apply thio correction if a denoicont is not used.


6.2.2  Desorptton Efficiency - Desorption efficiency  (DE)  for recovery of a speci-
fic compound  using  a certain solvent  from an adsorption tube  is calculated using
the following equation.


                   Qr -B
          DE  =  -                                             Equation 6-3
where

     Qr  =  Average peak area for spiked tubes,
     Qa  =  Average peak area for spiked solutions, and
     B   =  Average peak area for media blanks.


6.3-3  Concentration of Organic in Sample - The concentration (C) of the organic in
the sample in milligrams per dry  standard  cubic meter  or micrograms per dry stand-
ard liter (mg/dscm or ug/dsL)  is calculated using the following equation.
                                                                                       o

-------
     c  =
             (Wf + Wb - Bf - Bb)K
                                                                 Section No. 3.16.6
                                                                 Date June 30, 1988
                                                                 Page 3
                                                                  Equation 6-4
where
     B.
K
V.td,

DE
          dry
=  Mass of organic found in primary sorbent section,  ug,
=  Mass of organic found in backup sorbent section, ug,
=  Mass of organic found in primary section of average media
   blank, ug,
=  Mass of organic found in backup section of average media
   blank, ug,
=  Dilution factor, if applicable (for a 10 to 1 dilution, K = 10),
=  Sample volume corrected to standard conditions and a dry
   basis, L, and
=  Desorption efficiency, decimal value.
6.2.4   Conversion  to ppm  -  To  convert  the concentration  in milligrams  per dry
standard  cubic  meter  (micrograms per dry  standard liter)  to ppm,  the following
equation can be used.
       ppn
where
     C
     MW
          24.055 (dsL/g-mole gas)  x C
                     MW
       Concentration of organic,  ug/dsL or mg/dscm,  and
       Molecular weight of organic,  ug/ug-mole.
                                                                       Equation 6-5

-------
                                SAMPLE CONCENTRATION
                      mm
K*  =  A/ A; .  _,   F/
               Cs Pr Tt Fr K

*If applicable.
                                                                 Section No. 3.16.6
                                                                 Date June 30, 1988
                                                                 Page *»
                                                                       Equation 6-1
                                                                                        o
          Figure 6.1.  Calculation form for GC analysis by gas injection.
                                                                                        O

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 jj                                                                      Section No. 3.16.6
*                                                                      Date June 30, 1988
                                                                        Page 5


                         SAMPLE VOLUME, DRY BASIS AT STANDARD CONDITIONS

       V,,  =	^-^_ . ^  L,   Pbar  =  _? JT^l • _2  mo Hg,

       T   =  3_ 0_ 0_ . D_  °K,   Bws"  =0._^_^,   K*=  _ _ • 	


                                P    V
                                 bar  m              i r~"   ».
       V.,, dpv  =  0.3858  	  =      £• & . 0   L             Equation 6-2
              "              T. (1 -Bwg/K)"                -

       *If applicable.
                                      DESORPTION EFFICIENCY
            DE  =  (Qr - B)/Qa  =  0 . __ _^                                  Equation 6-3


                                       SAMPLE  CONCENTRATION

       wp  -  .82 A-V.VB.   wb  =  j_ z_ o_ .   6_ ug,   Bp  =  ___ g_ us,

       Bb  -  ___ 0_ug,   V8td  =  __^£".f.L,  DE  =  O.f.£.
                        V8td
                                     =	3 fj_ .  J?_ og/dscm or ug/dsL       Equation 6-4
                                        CONVERSION TO PPM

        C  =   ___ .  _  mg/dscm or ug/dsL,   MW  =  __ ^ _^ .  _/  ug/ug-mole,
        C  „   =   '                 gas)  x C   =  _ J_ £ .  £  ppm         Equation 6-5
                         MW


               Figure 6.2.  Calculation form for GC analysis by liquid injection.

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                                                                 Section No.  3.16.6
                                                                 Date June 30,  1988
                                                                 Page 6
                                                                    o
                Table  6.1.   ACTIVITY MATRIX FOR CALCULATION CHECKS
Characteristic
Analysis data
form
Calculations
 Acceptance limits
All data and calcu-
tions are shown
Difference between
check and original
calculations should
not exceed round-off
error
Frequency and method
   of measurement
Visually check
Repeat all calcula-
tions starting with
raw data for hand
calculations; check
all raw data input
for computer calcu-
lations; hand calcu-
late one sample per
test
Action if
requirements
are not met
Complete the
missing data
Indicate errors
on calculation
form. Figure 6.1
or 6.2
                                                                                        O
                                                                                        o

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                                                                 Section No. 3.16.7
                                                                 Date June 30, 1988
                                                                 Page 1
7.0     MAINTENANCE
      The normal use of emission- testing equipment subjects  it  to corrosive gases,
 extremes in  temperature,  vibration,  and  shock.   Keeping  the equipment  in  good
 operating order over an extended period of time requires knowledge of the equipment
 and a program of routine maintenance which is performed quarterly  or after 2830 L
 (100 ft3) of operation,  whichever is greater.   In addition  to  the quarterly main-
 tenance,  a yearly  cleaning  of pumps and  metering  systems is  recommended.   Main-
 tenance  procedures for the  various  components  are  summarized in Table  7-1 at the
 end of the  section.  The following procedures are not required,  but are recommended
 to  increase the reliability  of the equipment.

 7.1  Pump

      Several  types of  pumps  may be used to perform Method 18;  the two most common
 are the  fiber vane pump  with in-line oiler and the  diaphragm pump.  The fiber vane
 pump requires a periodic check of the oiler  jar.  Its  contents should be translu-
 cent;  the oil should be changed if not translucent.  Use  the oil specified by the
 manufacturer.   If none is specified, use SAE-10 nondetergent oil.  Whenever a fiber
 vane pump starts  to run erratically  or during  the  yearly  disassembly,  the  head
 should be removed and the fiber vanes  changed.   Erratic  operation of a diaphragm
 pump is normally due to either a bad diaphragm (causing leakage) or to malfunctions
 of  the valves,  which should  be cleaned annually by complete disassembly.

 7.2  Dry  Gas Meter

     Dry  gas meters should be checked for excess oil or corrosion of the components
 by  removing the top plate every 3  months.   Meters should be disassembled and all
 components  cleaned and  checked whenever  the rotation  of  the dials  is  erratic,
 whenever  the  meter will  not  calibrate properly over the required flow rate range,
 and  during the yearly maintenance.

 7.3  Rotameter

     Rotameters should be disassembled and cleaned according to the manufacturer's
 instructions using only recommended  cleaning  fluids every  3  months or upon erratic
 operation .

 7.4  Manometer

     The  fluid  in  the manometers should be changed whenever  there is discoloration
 or visible matter in the fluid, and during the yearly disassembly.

 7-5  Sampling Train

     All  remaining sampling  train  components should be visually checked  every  3
 months and  completely  disassembled  and  cleaned  or replaced  yearly.    Many items,
 such as quick disconnects , should be replaced whenever  damaged  rather than checked
 periodically.  Normally,  the  best procedure for maintenance in the field is to  have
 on hand  another entire unit  such as a pump,  Tedlar bags and  containers,  or heated
 sample line rather than replacing individual  components.

-------
                                                                 Section No. 3.16.7
                                                                 Date June 30, 1988
                                                                 Page 2
7.6  Oas Chromatograph
o
     Maintenance activities and schedules for gas chromatographs are make and nodol
specific.   It  is  therefore recommended  that the  analyst consult  the  operator's
manual for instructions relative to maintenance practices and procedures.
                                                                                        O
                                                                                        o

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                                                    Section No.  3.16.7
                                                    Date June 30,  1988
                                                    Page 3
Table 7.1.  ACTIVITY MATRIX FOR EQUIPMENT MAINTENANCE CHECKS

Apparatus
Fiber vane
pump
Diaphragm
pump
Dry gas meter
Rotameter
Manometer
Sampling
train
components
Gas chroina-
tograph

Acceptance limits
In-line oiler
free of leaks
Leak- free valves
functioning properly
No excess oil,
corrosion, or er-
ratic rotation of
the dial
Clean and no erra-
tic behavior
No discoloration or
visible matter in
the fluid
No damage
See owner's manual

Frequency and method
of measurement
Periodically check
oiler jar; remove
head and change fiber
vanes
Clean valves during
yearly disassembly
Check every 3 mo. for
excess oil or corro-
sion by removing the
top plate; check
valves and diaphragm
yearly and whenever
meter dial runs erra-
tically or whenever
meter will not cal-
ibrate
Clean every 3 no. or
whenever ball does
not move freely
Check periodically
and during disassemb-
ly
Visually check every
3 mo.; completely
disassemble and
clean or replace
yearly
See owner's manual

Action if require-
ments are not met
Replace as
needed
Replace when
leaking or mal-
functioning
Replace parts as
needed, or replace
meter
Replace
Replace parts
as needed
If failure noted,
replace appro-
priate components
See owner's manual

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o
o
o

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                                                              Section No. 3.16.8
                                                              Date June 30, 1988
                                                              Page 1
8.0     AUDITING PROCEDURES
     An  audit  is  an  independent  assessment  of data  quality.   Independence  is
 achieved  if  the .  individual(s)  performing  the  audit  and their  standards  and
 equipment are  different  from  the  regular  field  team  and  their  standards  and
 equipment.   Routine quality assurance  checks  by  a field  team are  necessary  to
 generate good  quality  data, but they are not part of the auditing procedure.  Table
 8.1  at  the  end  of this  section  summarizes  the  quality assurance  functions  for
 auditing.
     Based on the requirements of Method 18  and  the results  of collaborative test-
 ing  of other Reference Methods, two specific performance audits are recommended:
         1. An  audit of the sampling and analysis of Method 18 is required for NSPS
           and recommended for other purposes.
         2. And audit of the data processing is recommended.
     It is suggested that a systems audit be  conducted  as specified  by the quality
 assurance coordinator  in addition to these performance audits.  The two performance
 audits and the systems  audit are  described in  detail in  Subsections  8.1 and 8.2,
 respectively.

 8.1  Performance  Audits

     Performance audits  are conducted  to  evaluate  quantitatively  the  quality  of
 data produced  by  the total measurement system (sample collection, sample analysis,
 and  data  processing).    It is  required  that cylinder  gas  performance  audits  be
 performed once during  every  NSPS  test utilizing Method 18 and  it  is recommended
 that a  cylinder  gas audit be  performed once during any enforcement  source test
 utilizing Method  18 conducted under regulations  other than NSPS.

 8.1.1   Performance  Audit of the Field Test - As  stated in Section 6.5 of 40 CFR 60,
 Appendix A,  Method  18, immediately after the preparation of the calibration curves
 and  prior to the  sample analysis, the analysis audit described in 40 CFR 61, Appen-
 dix  C,  Procedure 2: "Procedure for  Field Auditing  GC  Analysis,"  should  be per-
 formed.   The information required to document the  analysis  of  the  audit sample(s)
 has  been included  on  the example data  sheets shown in  Figures 8.1  and  8.2;  the
 complete text  of  the procedure  is reproduced  in Section  3.16.10.  The audit anal-
 yses shall agree  within 10 percent (or other  specified  value,  as explained below)
 of  the  true  value.   When available,  the  tester  may  obtain  audit  cylinders  by
 contacting: U.S. Environmental Protection Agency, Atmospheric Research and Exposure
 Assessment Laboratory,  Quality Assurance Division (MD-77B), Research Triangle Park,
 North  Carolina  27711•   Audit  cylinders  obtained  from a commercial gas manufacturer
 may  be used  provided that (i) the  gas  manufacturer  certifies the audit cylinder in
 a manner similar  to the procedure described in  40  CFR 61, Appendix  B,  Method 106,
 Section  5.2.3-It  and  (2)  the  gas  manufacturer obtains  an independent  analysis.
 Independent  analysis is  defined as  an analysis performed  by an individual  other
 than  the  individual who  performs  the  gas  manufacturer's  analysis,  while  using
 calibration standards  and analysis equipment  different from  those used for the  gas
 manufacturer's analysis.    Verification  is  completed  and  acceptable  when  the
 independent  analysis concentration is within  5  percent  of the  gas  manufacturer's
 concentration.

    Responsibilities of  the Audit  Supervisor - The primary responsibilities  of
 the  audit supervisor are to ensure that  the proper audit gas  cylinder (s)  are  or-

-------
                                                              Section No. 3.16.8
                                                              Date June 30, 1988
                                                              Page 2

dered and safe-guarded, and to interpret the results obtained by the analyst.
    When auditing sampling systems that do not  dilute  the stack gases during samp-
ling, the audit gases ordered must consist of the same organic compound(s) that are
being  tested;  for  emission  standards  on  a concentration  basis,  the  audit  gas
concentration!s)  must be in>tJierange of 25% to 2$Q% of the applicable standard. If
two  cylinders  are not  available,  then one  cylinder  can be used.   If  the audit
cylinder value is between  5  an^ 20 ppm, the agreement should be within 15 percent
of the stated audit cylinder value.  It is strongly recommended that audit cylinder
values below  5 ppm not be  used.   For  emission standards which  specify a control
efficiency, the concentration  of  the audit gases should be  in  the range of 25% to
250/£ of the expected stack gas concentration.   If two  cylinders are not available,
the audit can be conducted using one cylinder.
    The audit supervisor must  ensure  that  the audit gas  cylinder(s) are shipped to
the  correct  address,  and to  prevent vandalism, verify  that they  are  stored  in a
safe location  both  before  and after  the  audit.  Also,  the  audit cylinders should
not be analyzed when  the pressure drops below  200  psi.   The audit supervisor then
ensures that the audits are conducted as described below.
    The audit supervisor must  also interpret the audit results.  When the measured
concentration agrees within  10 percent (or 15  percent for cylinders between 5 and
20 ppm)  of the true value,  he directs the  analyst to begin analyzing the source
samples.    When  the measured  concentration does  not agree within  the specified
criterion, the analyst should  first recheck the analytical system and calculations,
and  then repeat  the  audit.   If  the analyst  fails  the  second audit,  the audit
supervisor  should have  knowledge of the  agency's policy  for  failure.    If  the
result(s) are close to the allowed percentage or a consistent bias is present, the
supervisor may wish to allow.the analyst use of a correction  factor to be applied
at a later date;  however,  the analyst  must  make a  significant  effort  to find the
discrepancy  and  correct it.   If the error  cannot be found, the audit supervisor
should allow analysis of the samples, and then  conduct the audit again.
    During the audit,  the  audit supervisor should  record the  appropriate cylinder
number(s), cylinder pressure(s)  (at  the end  of  the audit),  and the calculated con-
centrations  on the "Field  audit  report form",  Figure 8.1.   The individual being
audited must not, under any  circumstances,  be  told the actual audit concentrations
until  the  calculated  concentration^) have been submitted to  the audit supervisor
and are considered acceptable.
    When  auditing sampling  systems  that dilute the  emissions  during collection,
the  audit  gas  concentration  value used in the  calculations  can either be based on
(1)  the  undiluted  concentration using  the criteria  discussed  above  or  (2)  the
expected concentration of  the  gases  following  dilution during collection using the
same dilution factor as used for the emission samples.
    The audit  procedures that follow are presented  according to the type of samp-
ling  system used  to  collect  the organic  emissions  and  whether  the  samples  are
analyzed on-site or at the base laboratory at a later date.

    Container  (Bag,  Syringe,  and  Canister)  Sampling  with  On-site Analysis  -  The
cylinder gas performance audit for  rigid-container bag,  syringe, or canister samp-
ling with on-site analysis consists  of  an  on-site audit  just prior to the analysis
of the emission  samples.   The recommended procedures  for  conducting the audit are
as follows:
        1.  The audit  samples should be  collected  in the  type  of container that
            will be used during the sample collection.   However, to conserve on the
            use of  the audit gas(es), it is usually not  necessary to use the rest
            of the  sampling system  to  collect  the samples  for unheated container
 o
 o
o

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                                                         Section No. 3.16.8
                                                         Date June 30, 1988
                                                         Page 3
                            FIELD AUDIT REPORT

Part A. - To be filled out by organization supplying audit cylinders.
          1. Organization supplying audit sample(s) and shipping address
          2. Audit supervisor, organization, and phone number
4.
5-
6.
             Shipping instructions: Name, Address, Attention
             /tettit Te-yh'ni.  100 Pnke Avf,  SfevZ., /VC   - X~.Af.
             Guaranteed arrival date for cylinders -
             Planned shipping date for cylinders -
             Details on audit cylinders from last analysis

a. Date of last analysis. .....
b. Cylinder number 	
c. Cylinder pressure, psi 	
d. Audit gas (es) /balance gas..
e . Audit gas ( es ) , ppm 	


Low cone.
yW/C^gg
lOfrq.
IS'ltO
.£f^4.
...M....

High cone



• "z!%/*i
...M.....

Part B. - To be filled out by audit supervisor.
          1. Process sampled
             Audit location
2.
3-
4.
5-
             Name of individual audit
             Audit date 	
             Audit Results:


b. Cylinder pressure before audit, psi 	 	
d. Measured concentration, ppm
Injection #1* Injection #2* Average 	
e. Actual audit concentration, ppm
f. Audit accuracy:1

Percent1 accuracy =
Measured Cone. - Actual Cone. x 100
Actual Cone.

Low
cone.
cylinder
/£&f
. y 5"fc£ .
'/s~p d '
J.4)/*+0
<*.**


»**£-

High
cone.
cylinder
/06&
-%£&-
2l2O/2,S4v

&?•

KM

          1Results of two consecutive injections that meet the sample analysis
          criteria of the test method.

                  Figure 8.1.   Field audit report form.

-------
                                                              Section No. 3.16.8
                                                              Date June 30, 1988
                                                              Page 4

            sampling.  Problems related to the reaction or retention of the organic
            compounds will still occur in the container.  Other interferents in the
            stack gas such as water vapor and other organics will not be present in
            the audit  cylinders and thus,  related problems will not  be assessed.
            For heated container  systems,  it may be necessary  to use  the sampling
            system to collect the audit gas.   However,  if the gases must be heated
            to prevent condensation,  it  is likely that an  audit gas cylinder will
            not be available.
        2.  The audit  samples should remain  in the appropriate container approx-
            imately  the  same  length of  time  that  the  source samples  will  stay
            prior to analysis.   After! the preparation  of the calibration curve,  a
            minimum of two  consecutive  analyses of each  audit  cylinder gas should
            be conducted.   The  analyses  must agree within 5# of the average.   The
            audit results should  be calculated by the  analyst  (or representative)
            and given  to the audit  supervisor.   The audit  supervisor will record
            all the  information and data on the"Field  audit  report form" and then
            inform  the  analyst  of  the  status of  the  audit.   The equations  for
            calculation of error are included on the form.

    Container (Bag and Canister) Sampling with Off-site Analysis - For cylinder gas
performance  audits  associated  with rigid-container bag  or canister  samples  that
are analyzed off-site, it is  recommended  that the audit be conducted off -site just
prior  to  the emission test (if the agency  desires)  and then  repeated during the
off -site  sample  analysis as  a quality control measure.    The  use  of  the pretest
audit  will help  ensure  that  the  analytical  system will  be acceptable  prior  to
testing.   Alternatively, the  audit gas  can  be collected in the  appropriate con-
tainer  on-site  or off -site,  and  then analyzed just prior to  the  analysis  of the
field samples.  It is recommended that the tester fill at least  two containers with
the audit gas to guard against a leak causing a failed audit.  Since the use of the
performance audit is to  both assess and  improve  the data quality,  the use of the
pretest audit  will  provide  the tester /analyst with a  better  chance  of obtaining
acceptable data.  The recommended procedure for conducting the audit is the same as
above  with the exception   that  the audit  supervisor  will  likely  not  be present
during the audit and the data will be reported by telephone.

    Direct Interface  Sampling -  Since direct interface  sampling  involves on-site
analysis ,   the performance audit is  conducted on-site after  the calibration of the
GC and prior  to sampling.   The audit gas cylinder is attached  to  the  inlet of the
sampling  probe.   Two consecutive analyses  of the audit  gas must be within  5%  of
the average  of  the  two  analyses.   The tester /analyst  then  calculates  the results
and informs the audit supervisor.  The audit supervisor records all information and
results on the "Field audit report  form"  and  then informs the tester/analyst as to
the acceptability of the results.

    Dilution Interface Sampling -  Since  dilution interface sampling  involves  on-
site analysis, the performance  audit is  conducted on-site after the calibration of
the GC and prior to sampling.   If the  audit gas cylinder obtained has  a concentra-
tion near the  diluted sample concentration,  the  audit gas  is  introduced directly
into the  sample port on  the GC.  If the audit  gas cylinder  obtained has a concen-
tration close to  the expected  sample concentration, then the audit gas  is intro-
duced into the dilution  system.   The audit  supervisor may wish  to order one cylin-
der to assess both the dilution system and the analytical system and another cylin-
der to  assess  only  the  analytical  system.   Follow  the  same procedures  described
/^\
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                                                              Section No. 3.16.8
                                                              Date June 30, 1988
                                                              Page 5

 above  for  recording  the information and reporting the results.

    Adsorption Tube  Sampling - The analysis for adsorption tube sampling is usually
 conducted  off-site.   Therefore,  the audit analysis  is  conducted off-site.   Again,
 the recommended procedure  is  to  conduct  the  audit once prior to the test and again
 following   the  test.    Though  the  audit  sample  could be analyzed  by  direct
 injection,  the inclusion of the chromatogram printout in the report will prove that
 the  audit   results  were obtained  through adsorption tube  sampling and  a solvent
 extraction.   Alternatively,  the  audit  samples  can be collected on-site or off-site
 and then analyzed just prior to the analysis of the field samples.  Since the audit
 supervisor will likely not be present during the analysis, the results are reported
 by telephone.
    To  collect  the  audit  gas with the  adsorption  tube sampling  train,  connect a
 sample  "T" to the  line from the  audit  gas cylinder.   Place the  adsorption tube
 sampling system on one  leg of the  "T";  connect a rotameter to the other leg.  With
 the sampling system off,  turn on  the audit gas  flow until  the  rotameter  reads 2
 1pm. Turn  on the sampling system  and sample  the  audit gas  for  the specified run
 time.  Approximately 1 1pm should be discharged through the rotameter.

 8.1.2   Performance  Audit of Data Processing - Calculation errors are prevalent in
 processing data.  Data processing errors can be determined by auditing the recorded
 data on  the field "and  laboratory  forms.   The original  and  audit (check) calcula-
 tions should  agree within round-off error; if not, all of the remaining data should
 be  checked.  The data  processing may  also  be audited  by providing  the testing
 laboratory with specific  data sets (exactly as would appear  in  the field),  and by
 requesting that the  data  calculation be  completed and that the results be returned
 to the agency.  This audit is useful  in checking both computer programs and manual
 methods of data processing.

 8.2  Systems Audit

    A  systems audit  is  an on-site, qualitative inspection and review of the total
 measurement system  (sample  collection,  sample  analysis,  etc.).    Initially,  a
 systems audit is  recommended for  each  enforcement  source test,   defined  here as a
 series of  three runs at one source.   After the test team gains experience with the
 method, the frequency of auditing may be reduced — for example,  to once every four
 tests.
    The  auditor  should have  extensive background  experience in  source  sampling,
 specifically  with the  measurement system  being audited.    The  functions  of  the
 auditor are summarized below:
    1.  Inform the  testing team of the  results  of pretest audits,  specifying any
        area(s)  that need special attention or improvement.
    2.  Observe procedures  and techniques of the field team  during sample collec-
        tion.
    3.  Check/verify  records  of  apparatus calibration  checks and  quality  control
        used  in  the laboratory  analysis  of control  samples  from  previous  source
        tests, where applicable.
    4.  Record the  results of the audit, and forward them  with comments  to  the
        test  team  management  so  that  appropriate  corrective  action  may  be
        initiated.
    While  on  site,   the  auditor  observes  the  source  test  team's overall  perfor-
mance,  including the following specific operations:

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                                                              Section No. 3.16.8
                                                              Date June 30, 1988
                                                              Page 6

    1.  Conducting  the  GC  calibration  and conducting the performance audit (if the
        analysis is conducted on-site).
    2.  Setting up and  leak testing the sampling train.
    3.  Collecting  the  sample at a  proportional  rate (if applicable)  or constant
        rate at the specified flow rate.
    4.  Conducting the  final leak check and recovery of the samples.
    5.  Conducting  the  initial  and final  check on the dilution  system (if appli-
        cable) .
    6.  Sample  documentation procedures,  sample  recovery,  and  preparation  of
        samples for shipment (if applicable).
    7-  Conducting sample analyses (if conducted on-site).
Figure 8.2 is a suggested checklist for the auditor.
o
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                                                    Section No. 3.16.8
                                                    Date June 30, 1988
                                                    Page 7
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21. Desorption efficiency acceptable, > 50% recovery
22. Adequate peak resolution
23. Bags passed reaction check, less than 10% change
24. Bags passed retention check, less than 5% retained
25. Flowmeters recalibration acceptable
26. Temperature sensor recalibration acceptable

COMMENTS
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Figure 8.2.  Method 18 checklist to be used by auditors.

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                                                              Section No.  3.16.8
                                                              Date June 30,  1988
                                                              Page 8
             Table 8.1.  ACTIVITY MATRIX FOR AUDITING PROCEDURES
                                                                    o
Apparatus
Performance
audit of
analytical phase
Data processing
errors
Systems audit—
observance
of technique
 Acceptance limits
Measured relative
error of audit
samples less than
10% (or other stated
value) for both
samples
Original and checked
calculations agree
within round-off
error
Operational tech-
nique as described
in this section of
the Handbook
Frequency and method
   of measurement
Frequency; Once during
every enforcement
source test*
Method; Measure audit
samples and compare
results to true values
Frequency; Once during
every enforcement
source test*
Method; Independent
calculations starting
with recorded data
Frequency; Once during
every enforcement
source test* until
experience gained,
then every fourth
test
Method; Observation of
techniques assisted
by audit checklist,
Figure 8.1
Action if
requirements
are not met
Review operating
technique and
repeat audit
Check and correct
all data for the
audit period
represented by
the sampled data
Explain to team
their deviations
from recommended
techniques and
note on Fig 8.1
O
*As defined here,  a source test for enforcement of the NSPS comprises a series of
 runs at one source.  Source test for purposes other than enforcement of NSPS may
 be audited at the frequency determined by the applicable group.
                                                                                         O

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                                                               Section No. 3.16.9
                                                               Date  June 30, 1988
                                                               Page  1
9.0     RECOMMENDED  STANDARDS  FOR ESTABLISHING TRACEABILITY

     To  achieve  data  of desired  quality,  two essential  considerations  are
 necessary:    (1)  the measurement process must bu in a state of statistical control
 at the time of the measurement,  and  (2)   the  systematic errors,  when combined with
 the random  variation  (errors  or  measurment),  must  result  in  an acceptable
 uncertainty.   As  evidence in support  of good quality data, it  is  necessary to
 perform  qulaity control checks and independent  audits  of  the  measurement process;
 to document  these  data;  and  to  use materials,  instruments,  and  measurement
 procedures that can be traced to an apropriate standard of reference.

     Data must be  routinely obtained by repeat measurements of  standar reference
 samples  (primary,  secondary, and/or working standards)  and the establishment of a
 condition  of  process  control.   The   working  calibration  standards should  be
 traceable to standards of higher accuracy.

     Audit samples (as discussed in  Section 3-16.8) must  be used  to validate test
 results  for  compliance  determination purposes  and  are   recommendeed  as  an
 independent check  on the measurement process when the method is performed for other
 purposes.

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o
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                                                                                      Section No.  3-16.10
                                                                                      Date June  30,  1988
                                                                                      Page 1
10.0     REFERENCE   METHOD*
        Since  the  initial  promulgation  of  Method  18  in  1983   (48  FR,  48344  -  48360,
 10/18/83),  there have been a number  of  revisions  and  additions  to  the method.    In
 the  interest  of consistency  and clarity,  the  version  of Method  18  reproduced  here
 is  from   the   most   recent   edition   of  the   Code  of   Federal  Regulations  which
 incorporates all  promulgated  changes  to  this date.
METHOD IB—MEASUREMENT or GASEOUS OR-
  GAWIC CoMTOtmn EMISSIONS BV GAS CKRO-
  MATOORAPHY

Introduction
  This method should not be attempted by
persons  unfamiliar  with the performance
characteristics of gas chromatography. nor
by those persons who are unfamiliar with
source sampling. Particular  care should be
exercised In the area of safety concerning
choice of equipment and operation In poten-
tially explosive atmospheres.
1. Applicability and Principle
  1.1 Applicability.  This method applies to
the analysis of approximately 00 percent of
the total gaseous organlcs emitted from an
Industrial source. It does not include tech-
niques   to  Identify and   measure  trace
amounts of  organic compounds,  such as
those found In building air and fugitive
emission sources.
  This  method  will not determine com-
pounds that (1) are polymeric (high molecu-
lar weight). (2) can polymerize before analy-
sis, or (3) have very low vapor pressures at
stack or Instrument conditions.
  1.2  Principle.
  The major organic components of a gas
mixture are separated by gas chromatogra-
phy (GO  and Individually quantified by
flame lonization, photolonization,  electron
capture, or  other  appropriate  detection
principles.
  The retention times of  each separated
component  are  compared  with  those of
known  compounds  under identical condi-
tions. Therefore, the analyst confirms the
identity and approximate concentrations of
the organic  emission components before-
hand. With this Information, the analyst
then prepares  or purchases commercially
available standard mixtures  to calibrate the
GC under conditions identical to  those of
the samples. The analyst also determines
the need for sample dilution to avoid detec-
tor saturation, gas stream filtration to elimi-
nate paniculate matter, and prevention of
moisture condensation.
2. Range and Sensitivity
  2.1  Range. The range of  this method Is
from about 1 part per million (ppm) to the
upper limit governed by GC  detector satura-
tion or column overloading. The upper limit
can be extended by  diluting the stack gases
with an inert gas or by using  smaller gas
sampling loops.
  2.2 Sensitivity. The sensitivity limit for a
compound Is defined as the minimum de-
tectable concentration of that compound, or
the concentration that produces a slgn&l-to-
noise ratio of three to one. The minimum
detectable  concentration   Is  determined
during  the  presurvey calibration for each
compound.
3. Precision and Accuracy
  Gas chromatographlc techniques typically
provide a precision of 5 to 10 percent rela-
tive standard deviation (RSD), but an expe-
rienced GC operator with a reliable instru-
ment can readily achieve  6 percent RSD.
For thla  method, the  following combined
GC/operator values are required.
  (a)  Precision.  Duplicate  analyses  are
within 5 percent of their mean value.
  (b) Accuracy. Analysis results of prepared
audit samples are within 10 percent of prep-
aration values.
4. Interferences
  Resolution interferences that may occur
can  be  eliminated  by  appropriate  GC
column and detector choice or by shifting
the retention times through changes In the
column flow rate and the use of tempera-
ture programming.
  The analytical system is demonstrated to
b« essentially free from contaminants by pe-
riodically analyzing blanks that consist of
hydrocarbon-free air or nitrogen.
  Sample cross-contamination that  occurs
when high-level and low-level samples or
standards are analyzed alternately, is best
dealt with by thorough purging of the GC
sample loop between samples.
  To assure consistent detector response,
calibration gases are contained  In dry air.
To  adjust gaseous organic concentrations
when water vapor is present In the sample.
water vapor concentrations are determined
for those  samples, and a correction factor Is
applied.
S. Presurvey and Presurvey Sampling.
  Perform a presurvey for each source to be
tested. Refer to Figure 18-1. Some of the in-
formation can be collected  from literature
surveys and source personnel. Collect gas
samples that can be analyzed to confirm the
Identities  and approximate concentrations
of the organic emissions.
  5.1 Apparatus. This apparatus list also
applies to Sections 6 and 7.
'40  CFR 60,  Appendix  A,  Method 18, July 1,  198?, pages ?40  - ?69-

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                                                                                             Section  No.  3.16.10
                                                                                             Date  June  30,   1988
                                                                                             Page  2
  5.1.1 Tenon Tubing.  (Mention of trade
names or specific products does not consti-
tute endorsement by the U.8. Environmen-
tal   Protection  Agency.)  Diameter   and
length determined by connection require-
ments of cylinder regulators and the  OC.
Additional  tubing  Is necessary to connect
the OC sample loop to the sample.
  5.1.2 Gas Chromatograph. GO with suit-
able  detector,  columns, temperature-con-
trolled sample loop and valve assembly, and
temperature programable oven. If necessary.
The GC shall achieve  sensitivity require-
ments for the compounds under study.
  5.1.3 Pump. Capable of pumping 100 ml/
mln. For flushing sample loop.
  5.1.4 Flowmeters. To  measure flow rates.
  5.1.5 Regulators. Used on  EOS cylinders
for GC and for cylinder standards.
  5.1.6 Recorder. Recorder with linear strip
chart  Is minimum acceptable.  Integrator
(optional) Is recommended.
  5.1.7 Syringes. 0.5-ml, 1.0- and 10-mlcro-
liter sizes,  calibrated, maximum accuracy
(gas tight), for preparing calibration stand-
ards. Other appropriate sizes can be used.
  5.1.8 Tubing Fittings. To plumb GC and
gas cylinders.
  5.1.9 Septums. For syringe Injections.
  5.1.10 Glass Jars. If necessary, clean-col-
ored  glass  Jars  with  Teflon-lined lids for
condensatj sample collection. Size depends
on volume of condensate.
  5.1.11 Soap Film Flow Meter.  To deter-
mine flow rates.
  5.1.12 Tedlar Bags. 10- and 50-liter capac-
ity, for preparation of standards.
  5.1.13 Dry Gas Meter with Temperature
and Pressure Gauges. Accurate to ±2 per-
cent, for perparatlon of gas standards.
  5.1.14 Midget  Implnger/Hot  Plate As-
sembly. For preparation of gas standards.
  5.1.15 Sample Flasks. For presurvey  sam-
ples, must have gas-tight seals.
  5.1.16 Adsorption  Tubes.  If  necessary,
blank tubes filled with necessary adsorberd
(charcoal, Tenax,  XAD-2, etc.) for presur-
vey samples.
  5.1.17 Personnel Sampling  Pump.   Cali-
brated, for collecting adsorbent tube presur-
vey samples.
  5.1.18 Dilution  System. Calibrated, the
dilution system  Is to be constructed follow-
ing the specifications  of  an  acceptable
method.
  5.1.19 Sample Probes. Pyrex or stainless
steel, of sufficient length to reach centrold
of  stack, or a point no closer to the walls
than 1 m.
  5.1.20 Barometer. To measure barometric
pressure.
  5.2  Reagents.
  5.2.1  Dslonized Distilled Water.
  5.2.2  Methylene Dlchloride.
  5.2.3  Calibration Gases. A series of stand-
ards prepared for every compound of inter-
eat.
  5.2.4  Organic Compound Solutions.  Pure
(09.0 percent), or as pure as can reasonably
be obtained, liquid samples of all the organ-
ic compounds needed to prepare calibration
standards.
  5.2.5  Extraction Solvents. For extraction
of adsorbent  tube  samples In preparation
for analysis.
  5.2.6  Fuel. As recommended by the man-
ufacturer for operation of the GC.
  5.2.7  Carrier Gas.  Hydrocarbon  free,  as
recommended by the manufacturer for op-
eration of the detector and compatability
with the column.
  5.2.8  Zero Gas. Hydrocarbon free air or
nitrogen, to be used for  dilutions, blank
preparation, and standard preparation.
  5.3  Sampling.
  8.3.1  Collection of Samples with  Glass
Sampling Flasks. Presurvey samples can be
collected In precleaned 250-ml double-ended
glass sampling  flasks.  Teflon stopcocks,
without grease, are preferred. Flasks should
be cleaned as follows: Remove the stopcocks
from both ends of the flasks,  and wipe the
parts to remove any grease. Clean the stop-
cocks, barrels, and receivers with methylene
dlchloride. Clean all glass ports with a soap
solution, then rinse with tap and delonlzed
distilled water. Place the flask  In a cool
glass annealing furnace and apply  heat  up
to 500* C. Maintain at this temperature for
1 hour. Afte? this time period, shut off and
open the furnace to allow the flask to cool.
Grease the stopcocks with stopcock grease
end  return them  to the  flask receivers.
Purse the assembly with high-purity nitrcX*^*\
sen for 2 to 5 minutes. Close off the stoi     )
cocks  after purging  to  maintain a slIjtiL    J
positive nitrogen pressure. Secure the stop-*—'
cocks with tape.
  Presurvey samples can be obtained either
by  drawing the eases Into the previously
evacuated flask or by drawing the gases into
and purging the flask with a rubber suctlor.
bulb.
  5.3.1.1  Evacuated Flask Procedure. Use a
high-vacuum pump to evacuate the flask to
the capacity of the pump; then close off the
stopcock leading to the pump. Attach a 6-
mm outside diameter (OD) glass tee to the
flask  inlet with  a short piece of Teflon
tubing. Select a 6-mm OD borosillcate sam-
pling probe, enlarged at one end to a 12-mm
OD and of sufficient length to reach the
centrold of the duct to be sampled. Insert a
glass wool  plug In the enlarged end of the
probe to remove particulate matter. Attach
the other end of the probe to the tee with a
short piece of Teflon  tubing. Connect a
rubber suction bulb to the third leg of the
tee. Place the filter end of the probe at the
centrold of the duct, or at a point no closer
to the walls than 1 m, and  purge the probe
with  the rubber suction bulb.  After the
probe Is completely purged and filled with
duct eases, open the  stopcock to the grab
flask until the pressure In the flask reaches
duct pressure. Close off the stopcock, and
remove  the probe from the duct. Remove
the tee from the flask and tape the stop-
cocks to prevent  leaks  during shipment.
Measure and record the duct  temperature
and pressure.
  5.3.1.2  Purged Flask  Procedure.  Attach
one end  of the sampling flask to a rubber
suction  bulb. Attach the other end to  a 6
mm OD glass probe as described in

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                                                                                            Section No.  3.16.10
                                                                                            Date  June  30,  1988
                                                                                            Page  3
5.3.1.1. Place the filter end of the probe at
the centrold of the duct, or at a point no
closer to the walls than 1 m. and apply suc-
tion with the bulb to completely purge the
probe and flask. After the flask has been
purged, close off the stopcock near the suc-
tion bulb, and then close the stopcock near
the probe. Remove the probe from the duct,
and disconnect both the probe and suction
bulb. Tape the stopcocks to prevent leakage
during shipment. Measure and record the
duct temperature and pressure.
  5.3.2  Flexible  Bag Procedure. Tedlar  or
aluminlzed Mylar bags can also be used to
obtain the presurvey sample. Use new bags.
and leak check them before field use. In ad-
dition, check the bag before use for con-
tamination by filling it with nitrogen or air,
and analyzing the gas by GC at high sensi-
tivity. Experience indicates that it is desira-
ble to allow the  inert gas to remain in the
bag about 24 hours or longer to check for
desorption of organlcs from the bag. Follow
the leak check and sample collection proce-
dures given in Section 7.1.
  5.3.3  Determination of Moisture Content.
For combustion or water-controlled process-
es,  obtain the moisture content from plant
personnel  or by measurement  during  the
presurvey. If  the  source is  below 59'  C,
measure the wet  bulb and dry bulb tempera-
tures,  and calculate the moisture content
using a psychrometric chart. At higher tern
peratures, use Method 4 to determine the
moisture content.
  5.4  Determination  of  Static  Pressure.
Obtain the static  pressure from  the plant
personnel or measurement. If a type S pltot
tube and an  inclined manometer are  used,
take care to  align the pilot tube 90' from
the direction of  the flow. Disconnect one of
the tubes to the manometer, and read the
static pressure; note whether the reading is
positive or negative.
  5.5   Collection of Presurvey Samples with
Adsorption Tube. Follow Section 7.4 for pre-
survey sampling.
6. Analysis Development
  6.1   Selection of GC Parameters.
  6.1.1  Column Choice. Based on the initial
contact with plant personnel concerning the
plant process and the anticipated emissions,
choose a column that provides good resolu-
tion and rapid analysis  time. The choice of
an appropriate column can be aided by a lit-
erature search, contact  with manufacturers
of GC columns, and discussion with person-
nel at the emission source.
   Most column  manufacturers keep excel-
lent records of their products. Their techni-
cal service departments may  be able to rec-
ommend appropriate columns  and detector
type for  separating  the anticipated com-
 pounds, and  they may be able to provide In-
 formation on Interferences, optimum oper-
 ating conditions, and column limitations.
   Plants with analytical laboratories may
 also  be able to provide  information on ap-
 propriate analytical procedures.
   6.1.2 Preliminary GC Adjustment. Using
 the standards and column obtained In Sec-
 tion 6.1.1, perform initial tests to determine
 appropriate   GC  conditions  that provide
 good resolution and minimum  analysis time
 for the compounds of interest.
  6.1.3  Preparation of Presurvey Samples.
 If the samples were collected on an adsorb-
 ent, extract the sample as recommended by
 the manufacturer for removal  of the com-
 pounds with a solvent suitable to the type
 of QC analysis. Prepare other samples In an
 appropriate manner.
  6.1.4  Presurvey Sample Analysis. Before
 analysis, heat the presurvey sample to the
 duct temperature to vaporize any condensed
 material.  Analyze the samples by the GC
 procedure, and compare the retention times
 against those  of the calibration samples
 that contain the components expected to be
 In the stream. If any compounds cannot be
 Identified with certainty by this procedure.
 Identify them by other means such as GC/
 mass spectroscopy (GC/MS) or GC/lnfrared
 techniques. A  GC/MS  system is  recom-
 mended.
  Use the GC conditions determined by the
 procedures of Section 6.1.2 for the first in-
 jection. Vary the  GC parameters during
 subsequent Injections to determine the opti-
 mum settings.  Once the optimum settings
 have been determined, perform repeat Injec-
 tions of the sample to determine the reten-
 tion time of each compound.  To inject a
 sample, draw sample through the loop at a
 constant rate (100 ml/mln for  30 seconds).
 Be careful not to pressurize the gas In the
 loop. Turn off the pump and allow  the gas
 In the sample loop to come to ambient pres-
 sure. Activate the sample valve, and record
 Injection  time,  loop temperature,  column
 temperature, carrier flow rate, chart speed,
 and attenuator setting. Calculate the reten-
 tion time of each peak using the distance
 from injection to the peak maximum divid-
 ed  by  the  chart speed. Retention times
 should be repeatable within 0.5 seconds.
  If the concentrations are too high for ap-
 propriate   detector   response,  a   smaller
 sample loop or dilutions may be used for gas
 samples, and, for liquid samples,  dilution
 with solvent is appropriate. Use the stand-
 ard curves (Section  6.3)  to obtain an esti-
 mate of the concentrations.
  Identify  all  peaks  by  comparing  the
 known  retention times of compounds ex-
 pected to be in the retention times of peaks
 in the sample.  Identify any remaining un-
 identified  peaks  which -have  areas larger
 than 5 percent of the total using a GC/MS,
 or  estimation of  possible compounds by
 their retention times compared to  known
 compounds, with confirmation by further
 GC analysis.
  6.2  Calibration  Standards.  Prepare  or
 obtain enough calibration standards so that
 there are  three different concentrations of
 each  organic  compound  expected  to be
 measured in the source sample. For each or-
 ganic compound, select those concentrations
 that bracket the concentrations expected in
the source samples. A calibration standard
may contain more than  one organic com-
pound.  If  available, commercial cylinder
gases may be used if their  concentrations
have been certified by direct analysis.
  If samples are collected in adsorbent tubes
(charcoal,  XAD-2, Tenax, etc.), prepare or
obtain  standards In the same solvent  used
 for the sample extraction procedure. Refer
 to Section 7.4.3.

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                                                                                             Section  No.  3.16.10
                                                                                             Date June  30,   1988
                                                                                             Page 4
                                                                                                                              o
  Verify the stability of all standards for
 the time periods they are used. If gas stand-
 ards are prepared in the laboratory, use one
 or more of the following procedures.
  6.2.1  Preparation  of  Standards  from
 High  Concentration  Cylinder  Standards.
 Obtain enough high concentration cylinder
 standards to represent ail the organic com-
 pounds expected in the. source samples.
  Use these high concentration standards to
 prepare lower  concentration  standards by
 dilution, as shown by Figures 18-5 and  18-6.
  To  prepare the  diluted  calibration  sam-
 ples,  calibrated  rotameters are normally
 used to meter both the high concentration
 calibration gas and the diluent  gas. Other
 types of flowmeters and commercially avail-
 able dilution systems can also be used.
  Calibrate each flowmeter before use by
 placing It  between the diluent gas supply
 and suitably sized bubble meter, splrometer.
 or wet test meter. Record all data shown on
 Figure 18-4. While it is desirable to calibrate
 the cylinder gas flowmeter with cylinder
 gas, the available  quantity and  cost  may
 preclude it. The error Introduced by using
 the diluent gas  for calibration is insignifi-
 cant for gas mixtures of up to  1,000 to 2,000
 ppm of each organic component.
  Once the flowmeters are calibrated,  con-
 nect the flowmeters to the  calibration and
 diluent gas  supplies  using  0-mm  Teflon
 tubing. Connect the outlet side of the flow-
 meters  through  a connector to a leak-free
 Tedlar bag as shown in Figure  18-5.  (See
Section 7.1 for bag leak-check procedures.)
Adjust the gas flow to  provide the  desired
dilution, and fill the bag with sufficient gas
for OC calibration. Be careful not  to overfill
and cause the bag to apply additional pres-
sure on the dilution system. Record the flow
rates of both flowmeters, and the laborato-
ry temperature and atmospheric pressure.
Calculate  the concentration C. In ppm of
each organic in the diluted gas as follows:
               1C)
                  6
                <>   *
                            Eq.   18-1
where:
10'—Conversion to ppm.
X-Mole or volume fraction of the organic
    in the calibration gas to be diluted.
q»-Flow rate of the calibration gas to be di-
    luted.
q^x Diluent gas flow rate.
Single-stage dilutions should be used to pre-
pare calibration mixtures up to about 1:20
dilution factor.
  For greater dilutions,  a double dilution
system is recommended, as shown in Figure
18-6. Fill the Tedlar bag with the dilute gas
from the second stage. Record the laborato-
ry  temperature, barometric pressure,  and
static pressure readings. Correct the  flow
reading for temperature and pressure.  Cal-
culate the  concentration C, in ppm of the
organic in the final gas mixture as follows:
                                                                                                             Eq.    18-2
 Where:
 10*<> Conversion to ppm.
 X-Mole or volume  fraction of the organic
    In the calibration gas to be diluted.
 Ha -Flow rate of the calibration gas to be di-
    luted in stage 1.
 q^i-Flow rate of the calibration gas to be di-
    luted In stage 2.
 CU-Flow rate of diluent gas in stage 1.
 dA-Flow rate of diluent gas In stage 2.
  Further details of the calibration methods
 for flowmeters and the dilution system can
 be found in Citation 21 in the Bibliography.
  6.2.2  Preparation   of  Standards  from
 Volatile Materials. Record all data shown on
 Figure 18-3.
  6.2.2.1 Oas  Injection  Technique. This
 procedure  b  applicable  to organic com-
 pounds that exist entirely as a cas at ambi-
 ent  conditions. Evacuate a 10-liter  Tedlar
 bae that has passed a leak-check 
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                                                                                               Section No.  3.16.10,,
                                                                                               Date June 30,  1988
                                                                                               Page 5   f
  where:
  G.-Gas volume or organic  compound In-
     jected, ml.
  »•-Conversion to ppm.
  P.-Absolute pressure of syringe before In-
     Jectlon. mm He.
  T.-Ateolute temperature of syringe before
     Injection. '1C.
  V.-Gas volume Indicated by dry gas meter.
     liters.
  Y-Dry gas meter calibration  factor, dimen-
     sionleEs.
  P.-Absolute pressure of dry gas meter, mm
     Hg.
  T.-Absolute temperature of dry gas meter.
     •K.
  1000-Conversion factor, ml/liter.
   6.2.2.2  Liquid  Injection Technique.  Use
  the equipment shown in Figure 18-8. Cali-
  brate the dry gas meter as described in Sec-
  tion 6.2.2.1 with a wet test meter or a spl-
  rometer. Use  a  water  manometer  for the
  pressure gauge and glass. Teflon, braes, or
  stainless steel for all connections. Connect a
  valve to the inlet of the SO-llter Tedlar bag.
   To  prepare  the  standards,  assemble the
  equipment as shown in Figure  18-8,  and
  leak-check the system. Completely evacuate
  the bag. Fill the bag with hydrocarbon-free
  air, and evacuate the bag again. Close the
  inlet valve.
   Turn on the  hot  plate, and allow the
   ,ter to reach boiling, Connect the bag to
   s  impinger outlet.  Record  the  Initial
   'eter reading, open the bag inlet valve, and
 open the cylinder. Adjust the rate  so that
 the bag will be completely filled in approxi-
 mately 15 minutes.'Record meter pressure
 and temperature, and local barometric pres-
 sure.
   Allow the liquid organic to equilibrate to
 room temperature.  Fill the 1.0- or 10-micro-
 liter syringe to  the desired liquid  volume
 with the organic. Place the syringe needle
 Into the impinger inlet using the  septum
 provided, and Inject the liquid Into the flow-
 Ing air stream. Use a needle of sufficient
 length to permit  Injection  of the  liquid
 below  the air inlet branch  of  the tee.
 Remove the syringe.
   When the bag is filled, stop the pump, and
 close the bag  inlet valve. Record the final
 meter reading, temperature, and pressure.
   Disconnect  the bag from the  Impinger
 outlet, and either set it aside for at  least 1
 hour, or massage the bag to Insure complete
 mixing.
  Measure the solvent liquid  density  at
room temperature by accurately weighing a
known volume of the material on an analyt-
ical balance to  the nearest 1.0 milligram. A
ground-glass  stoppered  25-mil   volumetric
flask or a glass-stoppered  specific gravity
bottle is suitable for weighing. Calculate the
result in terms of g/ml. As an alternative,
literature values of the density of the liquid
at 20 *C may be used.
  Calculate each  organic standard concen-
tration C. in ppm as follows:
Lv D  (24.055 x 106)
 M
                 100°
                           =   6.24  x 10
                                                  Y  P
                                            Eq.   18-4
            where:
            L,-Uquid volume of organic injected, pi.
            pi-Liquid organic density as determined, E/
               ml.
            M« Molecular weight of organic, g/g-mole.
            24.055-Ideal gas molar volume at 293 *K
               and 760 mm He, liters/g-mole.
            101-Conversion to ppm.
            1CCO-Conversion factor, jd/mL
              6.3  Preparation of  Calibration Curves.
            Establish proper GC conditions, then flush
            the campling loop for 30 seconds at a rate of
            100 ml/mln. Allow the sample loop pressure
            to equilibrate to atmospheric pressure, and
            activate the injection valve.  Record  the
            standard concentration, attenuator factor,
            injection time, chart speed, retention time.
            peak area, sample loop temperature, column
            temperature, and  carrier  gas  flow  rate.
            Repeat the standard Injection until two con-
            secutive Injections give area counts within S
            percent of their average. The average value
            multipled by the attenuator factor is then
            the calibration area value for the concentra-
            tion.
             Repeat this procedure for each standard.
            Prepare a  graphical plot of concentration
            (C,) versus the calibration area values. Per-
            form  a regression analysis, and draw  the
            least squares line.
             6.4  Relative Response Factors. The cali-
            bration curve generated from the standards
            for a single organic can usually be related to
            each of the Individual GC response curves
            that are developed In the laboratory for all
            the compounds In the source. In the field,
            standards for that single organic can then
            be used to "calibrate" the GC for all the or-
            ganics  present. This procedure should first
            be confirmed in the laboratory by preparing
            and analyzing calibration standards contain-
            ing multiple organic compounds.
             6.5  Quality Assurance  for  Laboratory
           Procedures. Immediately after the prepara-
           tion of the calibration curves and prior to
           the presurvey sample analysis, the analysis
           audit described In 40 CFR Part 61. Appen-
           dix C, Procedure 2: "Procedure for Field Au-
           diting OC Analysis," should be performed.
           The information required to document the
           analysis of  the audit samples has  been  In-
           cluded on the example data sheets shown in
           Figures 18-3  and 18-7. The audit  analyses
           should  agree  with the audit concentrations
           within  10  percent.  When  available,  the
           tester  may  obtain audit cylinders by con-
           tacting: U.S. Environmental  Protection
           Agency, Environmental Monitoring Systems

-------
 Laboratory.  Quality  Assurance  Division
 (MD-77), Research  Triangle  Park,  North
 Carolina  27711.  Audit cylinders obtained
 from a commercial gas manufacturer may
 be used provided that (a) the gas manufac-
 turer  certifies  the audit  cylinder In  a
 manner similar to the procedure described
 In 40 CFR Part 61. Appendix B, Method 108.
 Section 5.2.3.1, end (b) the gas manufactur-
 er obtains an Independent analysis of the
 audit cylinders to verify this analysis. Inde-
 pendent analysis Is defined as an analysis
 performed by an Individual other than the
 individual who performs the eta manufac-
 turer's  analysis,  while  using  calibration
 standards and analysis equipment different
 from those used for the gas manufacturer's
 analysis.  Verification is complete and  ac-
 ceptable  when the Independent  analysis
 concentration is within S percent of the fas
 manufacturer's concentration.
 7. Final Sampling and Analytit Procedure
  Considering  safety (flams hessrds)  and
 the source conditions, select an appropriate
 sampling and  analysis procedure (Section
 7.1,7.2,7.3, or 7.4). In situations where & hy-
 drogen flame la a hazard and no intrinsical-
 ly safe OC is suitable, use the flexible bag
 collection technique or an adsorption tech-
 nique. It the source temperature is below
 100'C, and the organic concentrations are
 suitable for the detector to be used, use the
 direct Interface method. If the source cases
 require dilution, use a dilution Interface and
 either the bag sample  or adsorption tubes.
 The choice between these two  techniques
 will depend on the physical  layout of the
 site, the source temperature, and the stor-
 age  stability  of the compounds If collected
 in the  bag.  Sample polar compounds  by
 direct interfacing or dilution Interfacing to
 prevent sample loss by adsorption on  the
 bag.
  7.1 Integrated Bag Sampling and Analy-
 sis.
  7.1.1 Evacuated Container Sampling Pro-
 cedure. In this procedure, the bags are filled
 by evacuating the rigid air-tight containers
 that hold the bags. Uss a field sample data
 sheet as shown In Figure 18-10. Collect trip-
 licate sample from each sample location.
  7.1.1.1  Apparatus.
  7.1.1.1.1 Probe.  Stainless  steel,  Pyrex
 glass, or Teflon tubing probe, according to
 the  duet temperature, with  6.4-mm  OD
 Teflon tubing of sufficient length to con-
 nect to the sample bag. Use stainless steel or
Teflon unions to connect probe and sample
line.
  7.1.1.1.2 Quick Connects.  Male  (2) and
female (2) of stainless steel construction.
  7.1.1.1.3 Needle  Valve. To  control  CM
flow.
  7.1.1.1.4 Pump.  Leakless  Teflon-coated
diaphragm-type pump or equivalent. To de-
liver at least 1 liter/mln.
  7.1.1.1.6  Charcoal Adsorption Tube. Tube
filled with activated charcoal, with glass
wool plugs at each end, to adsorb organic
vapors.
  7.1.1.1.6 Flowmet«r.  0 to  800-ml flow
range:   with   manufacturer's  calibration
curve.
                                                                                            Section  No.  3.16.10
                                                                                            Date  June  30,  1988
                                                                                            Page  6
  7.1.1.2  Sampling Procedure. To obtain a
sample, assemble the sample train as shown
in Figure 18-0. Leak check both the bag and
the  container.  Connect  the vacuum line
from the needle valve to the Teflon sample
line  from the probe. Place the end of the
probe at the centrold of the stack, or at a
point no closer to  the walls than 1 m, and
start the pump with the needle valve adjust-
ed to yield a flow of 0.5 liter/minute. After
allowing sufficient time to purge the line
several times, connect the vacuum line to
the bag, and evccuate until the rotamcter
Indicates no flow. Then position the sample
and  vacuum  lines  for sampling,  and  begin
th« actual sampling, keeping the rate pro-
portional to the Bluet velocity. As a precau-
tion, direct the gas exiting the rotameter
away from sampling personnel. At the end
of the sample  period, shut off  the pump,
disconnect the sample line from the bag,
and  disconnect the vacuum line from the
bag  container. Record the source tempera-
ture, barometric pressure, ambient tempera-
ture, sampling flow rate,  and Initial  and
final sampling time on the data sheet shown
in Figure 18-10. Protect the Tedlar bag and
Ito container from sunlight. When possible,
perform  the analysis  within 2  hours of
sample collection.
  7.1.2 Direct Pump  Sampling  Procedure.
Follow 7.1.1, except place the  pump  and
needle valve between the probe and the bag.
Ues a pump and needle valve constructed of
stainless steel or some other material not af-
fected by  the  stack gas. Leak  check the
system,  end then purge  with  stack gas
before the connecting  to the  previously
evacuated bag.
  7.1.3 Explosion  Risk Area Bag Sampling
Procedure. Follow 7.1.1 except replace the
pump  with  another evacuated  can (see
Figure 18-Oa). Use this method whenever
there Is a possibility of an explosion due to
pumps, heated  probes, or  other  flame pro-
ducing equipment.
  7.1.4 Other Modified Bag Sampling Pro-
cedures. In the event that condensation  is
observed in  the bag while collecting the
sample and a direct interface system cannot
be used, heat the bag during collection, and
maintain It at a suitably  elevated tempera-
ture   during  all  subsequent  operations.
(Note: Take care to leak check the system
prior to the dilutions so as not to create a
potentially explosive atmosphere.) As an al-
ternative, collect the sample gas, and simul-
taneously dilute It in the Tedlar bag.
  In  the first procedure, heat the box con-
taining the sample bag to the source tem-
perature, provided the components of the
bag and the surrounding box can withstand
this temperature. Then transport the bag as
rapidly as  possible to  the analytical area
while maintaining  the heating, or cover the
box with an Insulating blanket. In the ana-
lytical area, keep the box  heated to source
temperature until analysis. Be sure that the
method of  heating the box and the control
for the heating circuit are compatible with
the safety restrictions required in each area.
                                          o
o
                                                                                                                          o

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                                                                                            Section  No.  3-16.10
                                                                                            Date  June  30,  1988
                                                                                            Page  7
  To use  the second  procedure, preflll the
Tedlar bag with a known quantity of Inert
etas. Meter the Inert gas Into the bag accord-
Ing to the procedure for the preparation of
gas  concentration standards  of  volatile
liquid materials (Section 6.2.2.2). but elimi-
nate the midget Impincer section. Take the
partly filled bag to the source, and meter
the source gas Into the bag through heated
sampling  lines  and a heated flowmeter. er
Tenon  positive displacement pump. Verify
the  dilution factors periodically through di-
lution and analysis of gases of known con-
centration.
  7.1.5  Analysis Of Bag Samples.
  7.1.5.1  Apparatus. Same as Section 5. A
minimum of three gas standards  are  re-
quired.
  7.1.5.2  Procedure. Establish proper OC
operating conditions as described in Section
6.3. and record all data listed in Figure 18-7.
Prepare the GC so that gas can be drawn
through the sample valve. Flush the sample
loop with gas from one of the three calibra-
tion  mixtures,  and   activate  the  valve.
Obtain at least two chromatograms for the
mixture. The results  are acceptable when
the peak  areas from two consecutive Injec-
tions agree to within 5 percent of their aver-
age.  If they do  not, run additional analyses
or correct the  analytical techniques  until
this  requirement is met. Then analyze the
other two calibration mixtures in the  same
manner. Prepare a calibration curve as de-
scribed In the same manner. Prepare a cali-
bration curve as described In Section 6.3.
  Analyze the source  gas samples by con-
necting each bag to the sampling valve with
a piece of Tenon tubing Identified for that
bag. Follow  the specifications on replicate
analyses specified for  the calibration gases.
Record  the data listed in Figure 18-11. If
certain Items do not apply, use the notation
"N,A." After all  samples have  been ana-
lyzed, repeat the analyses of the calibration
gas mixtures, and generate a second calibra-
tion curve. Use an average of the two curves
to determine the sample gas concentrations.
If the two calibration curves differ by more
than 5 percent from their mean value, then
report the final results by  comparison to
both calibration curves.
  7.1.6 Determination  of Bag Water Vapor
Content. Measure and record  the ambient
temperature and barometric pressure  near
the  bag.  From a  water saturation vapor
pressure table,  determine and record the
water vapor content  as a decimal figure.
(Assume the relative humidity to be 100 per-
cent unless a lesser value  Is  known.) If the
bag has been maintained at an elevated tem-
perature as described In Section 7.1.4, deter-
mine the stack gas water content by Method
4.
  7.1.7 Quality  Assurance.   Immediately
prior to the analysis of the  stack gas  sam-
ples, perform audit analyses  as described In
Section  6.5. The audit  analyses must agree
with the audit concentrations within 10 per-
cent. If  the results are acceptable, proceed
with the analyses of the source samples. If
they do not agree  within  10 percent,  then
determine the reason  for the discrepancy,
and  take corrective action before proceed-
ing.
d-Bws)
                   18-5
  7.1.8  Emission Calculations. From the av-
erage calibration curve described In Section

7.1.5., select the value of C, that corresponds
to the peak area. Calculate the concentra-
tion C, In ppm, dry basis, of each organic In
the sample as follows:

c   -     csprT1Fr
LC  "  TT

where:
C.- Concentration of the organic from the
   calibration curve, ppm.
P,«Reference  pressure,  the  barometric
   pressure or absolute  sample  loop pres-
   sure  recorded  during calibration,  mm
   Hg.
TI-Sample loop temperature at the time of
   sample analysis, 'K.
Fr-Relative response factor (if applicable,
   see Section 6.4).
Pi-Barometric  or  absolute sample loop
   pressure at time of sample analysis, mm
   Hg.
T,-Reference temperature, the tempera-
   ture of the sample loop recorded during
   calibration,'K.
B.," Water vapor content of the bag sample
   or stack gas, proportion by volume.
  7.2  Direct Interface Sampling and Analy-
sis Procedure. The direct  Interface  proce-
dure can be used provided that the moisture
content of the gas  does not interfere with
the analysis procedure, the physical require-
ments of the equipment can be met  at the
site, and the source gas concentration Is low
enough that detector saturation  Is  not a
problem. Adhere to all safety requirements
with this method.
  7.2.1  Apparatus.
  7.2.1.1  Probe. Constructed  of  stainless
steel,  Pyrex glass, or Teflon tubing as re-
quired by duct temperature, 6.4-mm OD, en-
larged at duct end to contain  glass wool
plug. If necessary, heat the probe with heat-
Ins tape or a special heating unit capable of
maintaining duct temperature.
  7.2.1.2 Sample Lines. 6.4-mm OD Teflon
lines,  heat-traced to prevent condensation
of material.
  7.2.1.3 Quick   Connects.  To  connect
sample line to gas sampling valve on GC In-
strument and to pump unit used to with-
draw  source gas. Use a quick connect or
equivalent on the cylinder or bag containing
calibration gas to  allow  connection  of the
calibration gas to the gas sampling valve.
  7.2.1.4  Thermocouple  Readout  Device.
Potentiometer  or  digital  thermometer, to
measure source temperature and probe tem-
perature.
  7.2.1.5 Heated Gas Sampling  Valve. Of
two-position,  six-port  design,   to   allow
sample loop to be purged with source gas or
to direct source gas into the OC Instrument.
  7.2.1.6 Needle Valve. To control gas sam-
pling rate from the source.

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                                                                                             Section  No.   3.16.10
                                                                                             Date June  30,  1988
                                                                                             Page 8
                                              o
   7.2.1.7 Pump. Leakless Teflon-coated dia-
  phragm-type pump or equivalent, capable of
  at least 1 liter/minute sampling rate.
   7.2.1.0 Flowmeter.  Of suitable ranee to
  measure sampling rate.
   7.2.1.0 Charcoal Adsorber. To adsorb or-
  ganic vapor  collected  from the source to
  prevent exposure of personnel to source gas.
   7.2.1.10  Gas   Cylinders.   Carrier   gas
  (helium or nitrogen), and oxygen and hy-
  drogen for a flame lonization detector (FID)
  If one la used.
   7.2.1.11  Oas Chromatograph. Capable of
  being moved into the field, with detector.
  heated eta sampling valve, column required
  to complete separation of desired compo-
  nents, and option for temperature program-
  ming.
   7.2.1.12  Recorder/Integrator. To record
  results.
   7.2.2  Procedure. To obtain a sample, as-
  semble  the sampling  system as shown in
  Figure 18-12. Make sure all connections are
  tight. Turn on the probe and sample line
  heaters. As the  temperature of the probe
 and heated line approaches the source tem-
 perature as Indicated on the thermocouple
 readout device, control the heating to main-
 tain  a temperature of 0 to 3'C above  the
 eource temperature. While the probe and
 heated line are being heated, disconnect the
 sample line from the gas sampling valve,
 and attach the line from the calibration gas
 mixture. Flush the sample loop with  cali-
 bration gas and  analyze a portion of  that
 tnsa. Record the  results. After  the calibra-
 tion gas sample has been Hushed into the
 OC Instrument, turn the gas sampling valve
 to flush position, then reconnect the probe
 sample line to the valve. Place  the inlet of
 the probe at the centroid of the  duct, or at a
 point no closer to the walls than 1 m, and
 draw source gas into the probe,  heated line,
 and sample loop. After thorough flushing,
 analyze the sample using the same condi-
 tions as for the  calibration gas  mixture.
 Repeat  the  analysis  on  an  additional
 sample. Measure the peak areas for the two
 samples, and If they do not agree to within 8
 percent of their mean value, analyze addi-
 tional samples  until two consecutive analy-
 ses meet this  criteria.  Record the data.
 After  consistent   results   are  obtained,
 remove the probe from the source and ana-
 lyze  a  second calibration  gas  mixture.
 Record this calibration data and the other
 required  data  on the data  sheet shown in
 Figure 18-11. deleting the dilution gas infor-
 mation.
  (Non: Take care to draw all samples, cali-
 bration mixtures,  and  audits through  the
sample loop at the same pressure.)
  7.2.3 Determination  of Stack Gas Mois-
 ture Content. Use Method 4 to measure the
stack gas moisture content.
  7.2.4 Quality Assurance. Same as Section
 7.1.7.  Introduce  the audit  gases  in  the
 sample  line  immediately  following  the
 probe.
  7.2.5 Emission Calculations. Same as Sec-
 tion 7.1.8.
  7.3  Dilution  Interface  Sampling  and
 Analysis  Procedure.  Source samples  that
 contain a high concentration of organic ma-
 terials may require dilution prior to analysis
 to prevent saturating the OC detector. The
 apparatus required for this direct interface
 procedure is basically  the same as that de-
 scribed In the Section 7.2, except a dilution
 system is added between the heated sample
 line and the gas sampling valve. The appa-
 ratus is  arranged  so that either a 10:1  or
 100:1 dilution of the source gu can be di-
 rected to the Chromatograph. A  pump  of
 larger capacity  is also required,  and this
 pump must  be  heated and placed in the
 system between the sample  line and the di-
 lution apparatus:
  7.3.1 Apparatus. The equipment required
 in addition to that specified for the direct
 Interface system is as follows:
  7.3.1.1  Sample  Pump.  Leakless  Tenon-
 coated diaphragm-type that can withstand
 being heated to  120'C and deliver 1.5 liters/
 minute.
  7.3.1.2  Dilution Pumps. Two Model A-160
 Komhyr Teflon positive  displacement type
 delivering ISO cc/mlnute. or equivalent. As
 an option, calibrated flowmeters can be used
 In  conjunction with Teflon-coated  dia-
 phragm pumps.
  7.3.1.3  Valves. Two Teflon  three-way
 valves, suitable  for  connecting to 6.4-mm
 OD Teflon tubing.
  7.3.1.4  Flowmeters.  Two.  for  measure-
 ment of diluent gas, expected delivery flow
 rate to be 1.3SO cc/min.
  7.3.1.5  Diluent Oas with Cylinders  and
Regulators. Oas can  be  nitrogen  or clean
 dry air,  depending on the  nature of the
source gases.
  7.3.1.0  Heated Dox. Suitable  for being
 heated  to 120'C.  to  contain the three
pumps, three-way  valves, and  associated
connections. The box  should be  equipped
with quick connect fittings to facUitate con-
nection of: (1) The heated sample line from
 the probe, (2) the gas sampling valve. (3)
the calibration gas  mixtures, and (4) diluent
gas lines. A schematic  diagram of the com-
ponents and connections is shown in Figure
 18-13.
  (NOTE Care must be taken to leak check
the system prior to the dilutions so as not to
create a potentially explosive atmosphere.)
  The heated box shown  in  Figure 10-13  la
designed  to receive a heated line from the
probe. An optional  design is to build a probe
unit that attaches directly  to the heated
box. In this way, the heated box  contains
 the controls for the probe heaters, or. If the
 box is placed against the duct being sam-
 pled,  it may be possible  to eliminate the
 probe  heaters.  In  either case, a heated
 Teflon line Is used to connect the heated
 box to the gas sampling valve on the chro-
 ma tograph.
O
                                             o

-------
                                                                                             Section  No.  3.16.10
                                                                                             Date June  30,  1988
                                                                                             Page 9
    7.3.2  Procedure. Assemble the apparatus
  by connecting the heated  box, shown  in
  Figure  18-13. between the  heated sample
  line from the probe and the gas sampling
  valve  on  the chromatosraph.  Vent the
  source gas from the ges sampling valve dl-
  rectly to the charcoal filter,  eliminating the
  pump and  rot&meter.  Heat  the  sample
  probe, sample line, and  heated box. Insert
  the probe and source thermocouple to the
  centrold of the duct, or to a point no closer
  to the walla  than  1 m. Measure the source
  temperature, and adjust all beating units to
  a temperature 0 to 3'C above this tempera-
  ture. It this  temperature is  above the safe
  operating temperature of the Teflon compo-
  nents, adjust the heating to maintain a tem-
  perature high enough to prevent condensa-
  tion  of  water  and  organic compounds.
  Verify the operation of the dilution system
  by analyzing a high concentration  gas  of
  known composition through  either the 10:1
  or 100:1 dilution stages, as appropriate. (If
  necessary, vary the flow  of the diluent gas
  to obtain other dilution ratios.) Determine
  the concentration of the diluted calibration
  gxs using the dilution factor and the cali-
  bration curves prepared In the laboratory.
 Record the pertinent data on the data sheet
 shown in Figure 18-11. If the  data on the di-
 luted calibration era are not  within 10 per-
 cent of  the expected  values,  determine
 whether the chromatosreph or the dilution
 system la in error, and correct it. Verify the
 GC operation using a low  concentration
 standard  by  diverting the  gas into  the
 isjnple loop, bypaeting the dilution Byctem.
 If thesa analyzes are not  within acceptable
 limits, correct the dilution system to provide
 the desired dilution factors. Make this cor-
 rection by  diluting a  high-concentration
 standard gas mixture to adjust the dilution
 ratio as required.
   Once the dilution system and  QC oper-
 ations are satisfactory, proceed with  the
 analysis of source gas. maintaining yje gaxat
 dilution tattlnga as  used for the standards.
 Repeat the analyses until two consecutive
 values do not vary by more than S percent
 from their mean value are  obtained.
  Repeat the analysis of the calibration gat
 mixtures  to  verify  equipment  operation.
 Analyze the two field audit samples using
 either the dilution system, or directly con-
 nect to the gas campling valve as required.
 Record all data and report the results  to the
 audit supervisor.
  7.3.3  Determination of  stack Gas  Mois-
 ture Content. Same ta Section 7.2.3.
  7.3.4 Quality Assurance. Same as Section
 7.2.4.
  7.3.5  Emission Calculations. Same as  Sec-
 tion 7.2.5, with the dilution factor applied.
  7.4  Adsorption Tube Procedure (Alterna-
 tive Procedure). It  is  suggested that  the
 tester refer to the National Institute of Oc-
 cupational  Safety  and Health  (NIOSH)
 method for the particular organica  to be
 sampled.  The  principal  interferent will be
 water vapor.  If water vapor  is present at
 concentrations above 3  percent,  silica gel
 should be used In  front  of  the charcoal.
 Where more than one compound is present
in the  emissions, then develop  relative ad-
sorptive capacity information.
   7.4.1  Additional  Apparatus. In addition
  to  the  equipment  listed  in the  NIOSH
  method  for the particular orcanicKs) to bo
  sampled, the following items (or equivalent)
  are suggested.
   7.4.1.1  Probe  (Optional).   BoroslUcate
  glass or stainless steel, approximately 6-mm
  ID, with a heating system  if water conden-
  sation is a problem, and a filter (either in-
  stack or  out-stack heated to stack tempera-
  ture) to remove particulate matter. In most
  instances, a plug of glass wool is a eatisfac-
  tory filter.
   7.4.1.2  Flexible Tubing. To connect probe
  to adsorption tubes. Ues a material that ex-
  hibits *T»<"i™*i sample adsorption.
   7.4.1.3  Leakiest Sample Pump. Flow con-
 trolled. constant1 rate pump,  with a eet of
 limiting (sonic) orifices to provide pumping
 rates from approximately 10 to 100 cc/mln.
   7.4.1.4  Bubble-Tube Flowmeter. Volume
 accuracy within ±  1 percent, to calibrate
 pump.
   7.4.1.5  Stopwatch. To time »«pip""g and
 pump rate calibration.
   7.4.1.6  Adsorption Tubes. Similar to ones
 specified  by NIOSH. except the amounts of
 adsorbent per primary/backup sections ore
 eoo/aoo mg for charcoal tubas and KHO/2JO
 ms for dlica eel tubes. As an alternative.
 the tubes may contain a porous polymer ad-
 sorbent such &a Tenax GC or XAD-2.
   7.4.1.7  Barometer. Accurate to 5 mm Eg,
 to measure  atmospheric pressure  during
 sampling end pump calibration.
   7.4.1.8  Rotemeter.  0 to  100  cc/mln, to
 detect changes In flow rate during sampling.
  7.4.2  Sampling and Analyria. It is sug-
 gested that the tester follow the sampling
 and   analysis portion  of  the respective
 NIOSH method section  entitled "Proce-
 dure." Calibrate the pump and limiting ori-
 fice flow rate through adsorption tubes with
 the bubble tube flowmeter before campling.
 The sample system can be operated es a "re-
 drculatiaff loop" for this operation. Record
 the ambient temperature and barometric
 pressure. Then, during sampling, use the ro-
 tameter to verify that the pump and orifice
 sampling rate remains constant.
  Use a sample probe, if required, to obtain
 the sample at the centroid of the duct, or at
 a point no closer to the walls than 1 m. Min-
 imize the length of flexible tubing between
 the probe and adsorption  tubes. Several ad-
 sorption tubes can be connected in series, if
 the extra adsorptive capacity is needed. Pro-
 vide the gas sample to the sample system at
 a pressure sufficient for the limiting orifice
 to function as a sonic orifice. Record the
 total  time and  sample flow rate  (or the
 number of pump strokes), the barometric
 pressure, and ambient temperature. Obtain
 a total sample volume commensurate with
 the expected concentration^) of the volatile
 organlc(s)  present,   and  recommended
 sample loading factors (weight sample per
 weight adsorption media). Laboratory tests
 prior  to actual sampling may be necessary
 to predetermine  this volume.  When more
 than one organic is present In the emissions,
 then develop relative adsorptive capacity in-
 formation. If water vapor is present in the
sample at concentrations above 2 to 3 per-
cent, the adsorptive capacity may be severe-

-------
                                                                                            Section  No.  3.16.10
                                                                                            Date June  30,  1988
                                                                                            Page 10
                                           o
 ly reduced. Operate the gas chromatograph
 according to the manufacture's Instructions.
 Alter   establishing  optimum   conditions,
 verify  and  document  these  conditions
 during all operations.  Analyze the  audit
 samples (see Section 7.4.4.3), then the emis-
 sion samples.  Repeat the analyst* of each
 sample until the relative deviation of two
 consecutive Injections does not exceed 5 per-
 cent.
  7.4.3  Standards  and  Calibration.  The
 standards can be prepared according to the
 respective NIOSH method. Use a minimum
 of three different standards; select the con-
 centrations to bracket the expected average
 sample concentration. Perform  the calibra-
 tion before and after  each  day's sample
 analyses. Prepare the calibration curve by
 using the least squares method.
  7.4.4  Quality Assurance.
  7.4.4.1 Determination of Desorptlon Effi-
 ciency. During the testing program, deter-
 mine the desorptlon efficiency  In the ex-
 pected sample concentration range for each
 batch  of adsorption media to be used. Use
 an  Internal standard. A minimum desorp-
 tlon efficiency of 50 percent shall be ob-
 tained. Repeat  the  desorptlon  determina-
 tion until the relative deviation of  two con-
 secutive determinations does not exceed 5
 percent. Use the average  desorption  effi-
 ciency of these two consecutive  determina-
 tions for the correction specified In Section
 7.4.4.S.  If the desorptlon efficiency of the
 compound(s) of  Interest  Is questionable
 under actual sampling conditions, use of the
 Method of Standard Additions may be help-
 ful to determine this value.
  7.4.4.2 Determination  of Sample Collec-
 tion Efficiency. For the source samples, ana-
 lyze the primary and backup portions of the
 adsorption  tubes separately. If  the backup
 portion exceeds  10  percent  of the  total.
 amount (primary and backup), repeat the
 sampling with a larger sampling portion.
  7.4.4.3  Analysis   Audit.   Immediately
 before the sample analyses, analyze the two
 audits In accordance with Section 7.4.2.  The
 analysis audit shall  agree  with the audit
 concentration within 10 percent.
  7.4.4.4  Pump Leak  Checks and  Volume
 Flow Rate  Checks. Perform both of these
 checks immediately after sampling with all
 sampling train components in  place. Per-
 form all leak checks according to the manu-
 facturer's Instructions,  and record the re-
 sults. Use  the bubble-tube flowmeter to
 measure the pump volume now rate with
 the orifice  used in the  test sampling,  and
the result. If It has changed by more than 5
but less than 20 percent, calculate an aver-
age flow rate for the test. If the flow rate
has changed by more than 20 percent, reca-
librate the pump and repeat the sampling.
  7.4.4.5 Calculations. All calculations  can
be performed  according  to the  respective
NIOSH method. Correct all sample volumes
to standard conditions. If a sample  dilution
system has been used, multiply the results
by the appropriate dilution ratio. Correct all
results by dividing by the  desorptlon effi-
ciency  (decimal  value).  Report  results as
ppm by volume, dry basis.
  7.5  Reporting of Results. At the comple-
 tion  of  the field analysis  portion of  the
 study, ensure that the data sheets shown In
 Figure 18-11 have been completed. Summa-
 rize this data on the data sheets shown In
•Figure 18-15.
 8. Bibliopraphv
  1, American Society for Testing and Mate-
 rials. Ci Through C. Hydrocarbons in  the
 Atmosphere  by   Gas   Chromatography.
 ASTM D 2820-72. Part 23. Philadelphia, Pa.
 23:950-988.1673.
  2. Corazon, V. V. Methodology for Collect-
 Ing and  Analyzing  Organic  Air Pollutants.
 UJ3.   Environmental  Protection  Agency.
 Publication No. EPA-600/2-79-042. Febru-
 ary 1979.
  3.  Dravnieks,  A.. B. K. Krotoszynskl. J.
 Whltfleld, A. O'Donnell, and T. Burgwald.
 Environmental  Science  and  Technology.
 SU2):1200-1222.1971.
  4. Eggertsen. F. T., and F.  M. Nelsen. Oaa
 Chromatographic Analysis  of  Engine Ex-
 haust and Atmosphere. Analytical Chemis-
 try. J
-------
                                                                                         Section No.  3.16.10
                                                                                         Date June 30,  1988
                                                                                         Page 11
  19. NIOSH Manual of Analytical Methods.
 Volumes 1, 2, 3, 4, 5, 6, 7. U.S. Department
 of Health and Human Services National In-
 stitute for Occupational Safety and Health.
 Center for Disease Control. 4676 Columbia
 Parkway, Cincinnati.  Ohio  45226.  April
 1977-August 1981. May be available from
 the Superintendent of Documents. Govern-
 ment  Printing  Office, Washington,  DC
 20402. Stock Number/Price: Volume 1—017-
 033-00267-3/$13. Volume 2—017-033-00260-
 6/411.   Volume   3-017-033-00261-4/$l4,
 Volume  4—017-033-00317-3/S7.25, Volume
 5—017-033-00349-1/$10, Volume 6—017-033-
 00360-6/J9, and Volume 7—017-033-00386-
 5/$7. Prices  subject  to  change.  Foreign
 orders add 25 percent.
  20. Schuetzle. D.. T. J. Prater, and S. R.
 Ruddell.  Sampling and Analysis of Emis-
 sions from Stationary Sources; I. Odor and
 Total Hydrocarbons. Journal of the Air Pol-
 lution  Control  Association.  25(9):925-932.
 1975.
  21. Snyder, A. D., P. N.  Hodgson. M. A.
 Kemmer and J. R. McKendree. Utility of
 Solid Sorbents for Sampling Organic Emis-
sions  from Stationary Sources. U.S. Envi-
ronmental Protection Agency. Research Tri-
angle Park. NC  Publication No. EPA 600/2-
76-201. July 1976. 71 p.
  22.  Tentative  Method  for  Continuous
Analysis  of Total Hydrocarbons in the At-
mosphere. Intersociety  Committee,  Ameri-
can Public Health Association. Washington,
DC 1972.  p. 184-186.
  23. Zwerg, G.,  CRC Handbook of Chroma-
tography. Volumes I and II. Sherma. Joseph
(ed.). CRC Press. Cleveland. 1972.

-------
       cf
Ccntscts

Process to be
   Duct CP vsnt to ba i6=pled_
II. Process description
   Rsw oatertal
   Products
                                       Cats
                                          Pnsns
   Operating cycla
       Cheek:  Bitch	Continuous
       fining of batch or cyclo	
       Cist tics to test	
                                       .Cyclic
           Figure 18-1.  Prsllninary survey data sheet.
                                                               Cespenanta to bo  analysed    gxpaetod eoneantration
                                                               Suggoatad chxoaatogxaphie
Coltm flew rato     nl/nin   Hoad prosoora t
Colum toaparatnroi
     laothamal            *C
     Progra==3d fren      *C to _ 'C at _
Injaction port/aaopla  loop terrporaturo _ ^*C
Datactor  temperature        *C
Datactor  flow rataai Hydrogen _____nl/nin.
                                haad praaauro
                    Air/Osygen      nl/aia,
                                hoad pr a a aura
Chart apaed _________ inchea/ninuta
Cerpoond  datat
     Conpound      Ratantien tlna     Attanuatien
                                                                                                                     39
                                                                                                                      Hg
                                                                                                                   rsa Hg
                                                                                                                       TJ o C/)
                                                                                                                       £3 p CD
                                                                                                                       oq rf o
                                                                                                                       CD CD ct
                                                                                                                               O
                                                                                                                               P
                                                                                                                          fu
                                                                 7igara 10-2.  Chrcaatographic eonditiono  data ohaat.
                                                                                                                         0)  2!
                                                                                                                            O
                                                                                                                         CO •
                                                                                                                         o
                                                                                                                         -  OJ
                                                                                                                            CX>-
                                                                                                                            OO l
      O
                                                              o
                                                              o

-------
                 Preparation of Standards In Tedlar Bags
                          and Calibration Curve
                                                       Standards
                                              Mixture"  Mixture   Mixture
Standards Preparation Data:                      II         »2       13
  Organic:
  Bag timber or identification
  Dry gas ester calibration factor
  Final  neter reading (liters)
  Initial eater reading (liters)
  Hetered voluse (liters)
  Average eeter teaperature (*K)
  Average ester pressure, gauge (rai Hg)
  Average ataospherlc pressure (ea Hg)
  Average ester pressure, absolute (ea Hg)
  Syringe temperature (*X)
    (Section 6.2.2.1)
  Syringe pressure, absolute (ea Hg)
    (Section 6.2.2.1)
  YoTuae of gas In syringe (nl)
    (Section 6.2.2.1)
  Density of liquid organic (g/nl)
    (Section 6.2.2.2)
  Voluae of liquid In syringe ({!)
    (Section 6.2.2.2)

GC Operating Conditions:

  Stsple loop voline (•!)
  Saaple loop tesperature (*C)
  Carrier gas flow rate (tri/nln)
  Coluan tcsperature
    Initial CO
    Rate change PC/Bin)
    Final CCJ

Organic Peak Identification and
  Calculated'Concentrations:

  Injection ties (24-hr clock)
  Distance to paak (ca)
  Chart speed (ca/nln)
  Organic retention tiee  (nln)
  Attenuation factor
  Peak height (n)
  Peak area («2)
  Peak area x attenuation factor
  Calculated concentration (ppa)
    (Equation 18-3 or 18-4)

  Plot peak area x attenuation factor against calculated concentration
  to obtain calibration curve.

        rtgure 18-3.  Standards prepared In  Tedlar bags
                     and calibration curve.
                           Flcvatter Calibration
Flcwseter nusber or Identification	
Flowsteter type           	
Calibration device (x):Bubble raeter
Readings at laboratory conditions:
  Laboratory tesperature (Ti4(,)
                     Spl roaster
  Laboratory baresttrie pressure (Pi*b'
Flow data:
        	Flowseter
                                   Wet  testracier
                                   Hg
                             Calibration device
    reading ~| tesp.
  (as narked) I (*X)
i pressure
l(absolute)
 Titse I             I          ~
(nln) Igas voltaa*  jflow rate"
      T            I
      I             I
   a » Voluae of gas neasured by calibration device, corrected to standard
        conditions (liters).

   b * Calibration device gas volcee/tln*.

Plot f! wester reading against flow rate (standard conditions), and draw a
seooth curve.  If tns fletflMter being calibrated  1s • rottatter or otter
How device that Is viscosity dspenitnt, It wy be necessary to $tfier«tt a
•feally' of calibration curves that cover the operating pressure end
tcs?eraturt ranges of th» floustter.
      tla following technique should be verified before application. It nay
bt possible to calculate flow rat* readings  for rotczcters at standard
conditions Qjtd ts follows:
                     T1ab\ »«
                                             b\

                                             V
         Flew rata
  (lefearatcry cenditions)
                                  Ret* rat«
                             (standard conditions)
            Figure 18-4.  Flotewtw calibration.
                                                         TJ a to
                                                         CD Co (D
                                                         oq ci- o
                                                         to a> ct-
                                                               H-
                                                         I-1 «-4 o
                                                         UJ C O
                                                            ro s:
                                                               o
                                                            uo •
                                                            o
                                                                                                                                                                 VD a\
                                                                                                                                                                 <»•
                                                                                                                                                                 00 H'
                                                                                                                                                                     o

-------
                                                             Section No.  3.16.10
                                                             Date  June 30,  1988
                                                             Page  14
                                                                      o
    CAS
  CYUHMIl
   DILUENT
     CAS
   cnnron?
                  h«^

                  \
                        CALlDRATTDROTAf.'ITinS
                         nim ROB CONTROL
                              VAIVES
Flpjr» 1S-5.
                                 calfbritfra
o
                             men
                         co:;cniTnATio:i
                             DASTE
      mm—
                                 3—f,lEtJl£ VALVES
                                         J
                                   PRESSURE
                                                    ion
                                                    om
                                                    GAS
                       DIUmiTAIR
                                DIUKHTAin
PURESUGSTAtlCEOn
             MIXTURE
              Figure 10-6.  Tttostigs dllu.tlon epparatus.
                                                                                  O

-------
                                                                          Section  No.  3.16.10
                                                                          Date June  30,   1988
                                                                          Page 15
          Preparation of Standards by Dilution of Cylinder Standard

 Cylinder standard:  Organic	 Certified concentration	

 Standards Preparation Data:                            Date 	
ppa
              Stage 1                 Mixture 1     Mixture 2     Mixture 3

   Standard gas  flewmeter reading     	     	     	
   Diluent gas flowaeter reading             .       	     _____
   Laboratory  teaperature CK)        	     	
   Baresstrlc  pressure (o Hg)        	     	
   Flotottter gage pressure (IBS Hg)     	     	
   Flow rate cylinder gas at          	     	
    standard conditions (al/nln)
   Flow rate diluent gas at           	     	
    standard conditions (nl/raln)
   Calculated  concentration (ppa)      	     	

              Stage 2 (If used)

   Standard  gas flowaeter reading      	     	
   Diluent gas flowaater reading      	     	
   Flow rate stage 1 gas at           	     	
    standard conditions (al/nln)
   Flow rate diluent gas at           	     	
    standard conditions (ml/Bin)
   Calculated concentration (ppn)      	     	

 GC Operating Conditions:
   Sample  loop voluae (nl)             	    	
   Saaple  loop temperature  CO        	    	
   Carrier gas flow  rate  (nl/otn)      	    	
   Column tenperature:
        Initial CO                   		
       Prograa rate  CC/nln)             "~~~~        	
    ••:  F1nal (
-------
                                                           Section No.  3-16.10
                                                           Date  June 30,  1988
                                                           Page  16
                          COILING
                           WATER
                            OATH
                                           SYRINGE
                                            SEPTUM
                                            4- MIDGET
                                               IMPIKGER
                                    HOTPLATE
                    NITROGEN
                    CniNDER
                                                                                    o
                Figure 18-0.  Apparatus for preparation cf liquid eatcrlali.
                                                                      VZtJT
                         TIRO?!
          STACK
          HAU.

   FRTIR    fl
C31ASS HJOll 11
 nrvinst
 O-JIYPE
PITOTTUEE
                        RIGID UAKRJ007 (XWTAI
                                                                                    O
                Figure 10-9.   Integrated bag strpHng  train.

-------
      PrcSa
8* Tefla
   WstftClta?
                                                                       Section No. 3.16.1C
                                                                       Date June 30,  1988
                                                                       Page 17
Mr Tlfht Steal Crta „








«
p* 	 oHtpa 	 j
/--..
*:
:
' 0 1
\ ' :
« . •
% :
i
/
«._v









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                               18-9*. Exploslca risk CM (telling esthsd.
            P1«J»t_
            S1ta_
                                                      Oats
                                                   Simple g
            Source tcrpsraturo (*C)
                       Testtrrotca Hg)_
                   tc=?«ratara (*C)
            Sample flcy rate(eppr.)
            Dag mnbsr
            Start  tlcz
            Finish tlsa
                     Figure 18*10.  Field staple data sheet - Tedlar
                                bag collection catted.

-------
                                                                Section No. 3.16.10
                                                                Date June  30,  1988
                                                                Page 18
o
Plant..
Location
    Caneral 4nfornaU.cn
          Source t*Ep*raturo  (*C)
          Probe tarperatture CO
          AsMent tezporature  (*C)
          Atsoiphtrie praaaure  (ea)
          Coturce preaaero  (*Cg)
          Absolute eooreft prtaaura p««4  tea/nin)

          Dilation gas  flow rate  (al/ein)
          Dilution Ca«  nsad (tyebol)
          Dilution ratio
O
                HCJTV 16-11.  mid tnalyslt data stem.

a.  ?ield «aalynia Data - Calibration Cue
    Can ea.	            Tiia
                 Area   Attenuation   A x A Factor   Cene.
    torn Co.              tlea
                 Area   Attanaatien   A »e A Taeter   Cone,  (ppn)
    Ban  Bo.	   tlea
    Cenponanta   Area   Atttnuatien   A « A Factor   Cene.  (ppn>
                                                                                             O
              Flpirt 1>-11 (tcntlr.uad).  Flald analysis dau th«tu.

-------
                                                                Section  No.  3-16.10
                                                                Date  June  30, 1988
                                                                Page  19
TC
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i







H cssaters
(On Outside
Of eor.)
Row Rate Of
1350 cc/Ntn
                     Heated Box at 1ZO°C Or Source Temperature
Figure 18-13.  Schematic dlagraa of the heated box required
             for dilution of sarple gas.

-------
                                                                       Section No.   3.16.10/*—\
                                                                       Date  June 30,   1988 (     )
                                                                       Page  20                 V-X
   QACTOU* Oioinc BAxrwra jure AHALTIU
               GnrsLirT
                                                       floWOV   AoUTM    flOCfM
     Olcswod with Initial* or number u
              •pproprUte)                                 '       *~      <
                                        LO*a*nl
                                          Coorot
                                           tsaotntttn
 L rronrm dtu:

      B. Onb aaete utlTMd"                  <"c>-
        "    '               ~ ———      uoscnton
                                           CO	
                                          Ateiotpbcrte



 t t^aontorT rmKtrmrton data:                    Coaret
      X OtUbntiao curm pr»-
       puvd—_^	   O                _
           Number of eompo-                   (mlAami
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                                          CimpUloop
            conpootot (1 rv-                   U8p
      B. Aattt »«iTjil«i (opttoo-                  Csmpl*

           Amlnl> eonplM-                   UaM(M-lsr
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          BM*UI«I*____  a      a        rsurc/
                           a      o
          CdstJaa tnUrtJ6t_  Q      O        FtnttlCC}..
     B. ItmalMr of HB9>« eat-                 O»m«rf«a
                           tn              flovnl*
4. rwkl u^trttz                               Unl/BtoX
     X  TBttl  bjdi'oeiiton                 DtUctar
          KambCT of ersrapo-
      1S*14. fifnpllny tnd uulysli
                                       Ftrformod by Ulm»lnr«l-
 auxou* Otcunc Rtvnna uro Axu.Tti*    __
                DATA                   DU« -
                                           
                                           flow rmtc
pUnt	
pm                                   PUure 18-14. o«Bipaaj «ad (nairtli sheet.
                                                                                                  O

-------
                                                                                          Section No.  3.16.10
                                                                                          Date June 30,  1988
                                                                                          Page 21
     APPENDIX C—QUALITY ASSURANCE
                PROCEDURES*

    Procedure 1—Determination of Adequate
       ChromatosrrapMc Peak Resolution
    In this method of dealing with resolution.
  the extent to  which one chromatographic
  peak overlaps another la determined.
    For convenience, consider the ranee of the
  elution curve of each compound as running
  from -2
-------
                                                                                          Section  No.  3.16.10
                                                                                          Date  June  30,  1988
                                                                                          Page  22
                                                                                                                                 o
    C *fc_«_                k_
      b-JOj               b-to,            b*2of
                          -07            -07-
Th* following calculation ttept art r*qu1red:*
1.  2o$ « t./^ In 2
2.  oe • t£
3.  x, « (b
4.  x,
S.  fl(x,)»-i
              P-x*\
              "*" /dx
8.  A0 « IflAe/A,
9.  Pircentag* overlap « Afl x 100 ,
 A •
    AC «
    tc «
 C(xi) *
 Q(*«) *
    Ifl «
     Ar«a of th* i«tplt p«tk of Inttrtft daUralntd by tltctronlc inte-
     gration or by th* forcula A( » h t..
     Arta of th* contnlnant ptik, daunltttd In th* tax aanntr at A(.
     Olitane* on th* chrcutographfc chart that ttparatat the uxlu of
     thj two p«aki.
     Pttk h*1eht of th* ttspU coxpound of 1nt*r*>t, M*tur*d froa th*
     «v«r«j» vilu* of th* paialtn* to th» BUtnui of th* curv*.
     Width of ««cpU p*ak of InUrcit at 1/2 p*ak h**xJ«r preesur*. p«_
          ij/bdux
          D.ppm.
                                                                                                    lOKCone.
                                                                                                              It^l (JUflC.
                                                                                                                               o
                                                                               Part S.—To be filled out by audit mpetvl-
                                                                              sor.                        -    .    .
                                                                               I. Process sampled	
                                                                                2. Audit location-
                                                                               3. Name of individual audlt-
                                                                               4. Audit date	
                                                                               5. Audit results:


b. Cy£ndv pnMturt before audit, pet 	
c. Cy&ndor pf*»eur* after eurfit p*^ 	

fl* fc^ecton tC2* Avere^e
*. Actual audK eonoerrtratioa Ppm (Part A,
«•}... 	
f. Aucflecctncy:1
ImrCmw. Cyimtif
Hijfi Cwc, CV"^1** 	 	 	 	
Percent' aceureey -
Ueejind Conc-Actut* Cone.
AdudConc.
Q pfi^r"! 
-------
                                                         Section No. 3.16.11
                                                         Date June 30,  1988
                                                         Page 1
11.0   REFERENCES
 1.
 2.
 3.
 4.
     Method  18 -  Measurement of Gaseous Organic Compound - Emissions  by  Gas
     Chromatography.   Federal Register, Volume 48, No. 202, October 18,  1983 ,
     page
 5.
 6.
 7.
 8.
 9.
10.
11.
12.
     Amendments  to Method 18.  Federal Register, Volume 49, No. 105, May  30,
     1984, page  22608.

     Miscellaneous Clarifications  and Addition of Concentration Equations to
     Method  18.   Federal  Register. Volume 52, No. 33, February 19, 198?, page
     5105.

     Stability  of  Parts-Per-Million  Organic  Cylinder Gases and Results of
     Source  Test  Analysis  Audits,  Status  Report #8.  U. S. Environmental
     Protection   Agency Publication No. EPA-600/2-86-117, January 198?.  Also
     available from NTIS  as Publication No. PB 8y-l4l46l.

     Traceability  Protocol for Establishing True Concentration of Gases Used
     for  Calibration and Audits  of  Continuous  Source  Emission  Monitors
     (Protocol  No.   1).   Section  3-0.4, Quality Assurance Handbook, Volume
     III, Stationary Source Specific Methods, U. S. Environmental  Protection
     Agency  Publication No. EPA-600/4-?7-027b, June 15, 1978.

     Methanol,   Method  2000.  NIOSH Manual of Analytical Methods, Volume  2,
     Third Edition,  U.  S.  Department  of Health and Human Services, February
     1984.

     Alcohols  I, Method  1400.  NIOSH Manual of Analytical Methods, Volume 1,
     Third Edition,  U.  S.  Department  of Health and Human Services, February
     1984.

     Alcohols  II, Method  1401.  NIOSH Manual of Analytical Methods, Volume 1,
     Third Edition,  U.  S.  Department  of Health and Human Services, February
     1984.

     Hydrocarbons. BP 36  - 126° C, Method 1500.  NIOSH Manual  of  Analytical
     Methods,  Volume  2,  Third Edition, U. S. Department of Health and Human
     Services , February 1984 .

     Development  of Methods  for  Sampling 1,3-Butadiene.   Interim  Report
     prepared  under U.   S.  "Environmental Protection Agency Contract Number
     68-02-3993, March  1987-

     Hexachlorocyclopentadiene, Method  2518.   NIOSH  Manual  of  Analytical
     Methods,  Volume  2,  Third Edition, U. S. Department of Health and Human
     Services, February 1984.

     Method  110  - Determination of Benzene from  Stationary Sources, Proposed
     Rule.   Federal Register. Volume 45, No. 77, April 18, 1980, page 26677.

-------
                                                            Section No.  3.16.11
                                                            Date  June 30,  1988   >«.
                                                            Page  2              f   j

13.    Hydrocarbons,  Aromatic,  Method 1501.   NIOSH Manual  of Analytical Methods,
      Volume 2,  Third Edition, U.  S. Department  of  Health and Human Services,
      February 1984.

14.    Naphthylamines,  MetftG>a£li264.   NIOSH Manual of Analytical Methods, Volume
      4,  Second  Edition,  U.  S. Department of Health and  Human Services, August
      1978.

15.    Ketones I, Method 1300.   NIOSH Manual of  Analytical  Methods,  Volume 2,
      Third  Edition,  U.  S.  Department of Health and Human Services,  February
      1984.

16.    2-Butanone, Method  2500.   NIOSH Manual of Analytical Methods, Volume 1,
      Third  Edition,  U.  S.  Department of Health and Human Services,  February
17-   Ethylene Oxide, Method 1607.  NIOSH Manual of Analytical  Methods, Volume
      1, Third Edition, U. S. Department of Health and Human Services,  February
      1984.

18.   Propylene Oxide, Method 1612.  NIOSH Manual of Analytical Methods. Volume
      2, Third Edition, U. S. Department of Health and Human Services,  February
      1984.

19.   Hydrocarbons, Halogenated,  Method  1003.   NIOSH  Manual  of  Analytical
      Methods, Volume  2,  Third  Edition, U. S. Department of Health and Human
      Services, February 1984.

20.   Ethylene  Dibromide,  Method  1008.   NIOSH Manual of Analytical  Methods,
      Volume  1,  Third Edition, U. S. Department of Health and Human Services,
      February 1984.

21.   Method 23 - Determination of Halogenated Organics from Stationary Sources
      (proposed  method).  Federal Register. Volume 45. No. 114, June 11, 1980,
      page 39766.

22.  . 1,2-Dichloropropane,  Method  1013.   NIOSH Manual of Analytical  Methods,
      Volume  1,  Third Edition, U. S. Department of Health and Human Services,
      February 1984.

23.   Development  of Methods for Sampling Chloroforn and Carbon Tetrachloride.
      Interim Report prepared for U. S.. Environmental  Protection  Agency under
      EPA Contract Number 68-02-3993, November 1986.

24.   Dichlorodifluoromethane, Method 111.  NIOSH Manual of Analytical  Methods,
      Volume  2, Second Edition, U. S. Department of Health and Human Services,
      April 1977.
                                                                                O
                                                                                O

-------
                                                            Section No.  3.16.11
                                                            Date June 30, 1988
                                                            Page 3
25.   Methyl Bromide, Method 2520.  NIOSH Manual of Analytical  Methods, Volume
      2, Third Edition, U. S. Department of Health and Human Services,  February
      1984.

26.   Methyl  Chloride,  Method 99.  NIOSH Manual of Analytical Methods, Volume
      4, Second  Edition, U. S. Department of Health and Human Services, August
      1978.

27.   Butler, F. E., E. A. Coppedge, J. C. Suggs, J. E.  Knoll,  M.  R.  Midgett,
      A. L. Sykes, M. W. Hartiaan, and J.  L.  Steger.   Development of  a Method
      for Determination  of Methylene Chloride Emissions at Stationary  Sources.
      Paper  for  presentation at 80th Annual Meeting of Air Pollution   Control
      Association, New York, NY, June 1987.

28.   Vinylidene Chloride, Method 266.  NIOSH  Manual  of  Analytical  Methods,
      Volume  4, Second Edition, U. S. Department of Health and Human Services,
      August 1978.

29.   Ethyl Chloride,  Method 2519.  NIOSH Manual of Analytical Methods, Volume
      1, Third Edition, U. S. Department of Health and Human Services,  February
      1984.

30.   Method  106  - Determination of Vinyl Chloride from  Stationary  Sources.
      Federal Register, Volume 47, No. 173, September 7, 1982, page 39168.

31.   Knoll,  J.  E.,  M.  A. Smith, and M. R. Midgett.  Evaluation of  Emission
      Test Methods for Halogenated Hydrocarbons, Volume II, U. S. Environmental
      Protection Agency Publication No. EPA-600/4- 80-003,  January 19&0.

32.   Methylene  Chloride, Method 1005.  NIOSH Manual  of  Analytical  Methods,
      Volume 2, Third Edition, U. S. Department  of  Health and Human Services,
      February 1984.

33.   Tetrachloroethylene,  Method  335.   NIOSH  Manual of Analytical  Methods,
      Volume 3» Second Edition, U. S. Department  of Health and Human Services,
      April 1977-

34.   Trichloroethylene,  Method  336.   NIOSH  Manual  of   Analytical  Methods,
      Volume 3t Second Edition, U. S. Department  of Health and Human Services,
      April 1977.

35.   -1,1,2-Trichlorotrifluoroethane.  Method  129.   NIOSH  Manual of Analytical
      Methods,   Volume  2, Second Edition, U.  S. Department of Health and Human
      Services, April 1977-                                             .

36.   Vinyl Chloride, Method 1007.  NIOSH Manual of Analytical  Methods, Volume
      2, Third Edition, U. S. Department of Health and Human Services,  February
      1984.

37-   Mann, J.  B., J. J. Freal,  H.  F. Enos,  and J. X. Danauskas.  Development
      and  Application  of   Methodology   for   Determining   1,2   Dibromo-3-
      Chloropropane (DBCP) in Ambient Air.  Journal  of  Environmental   Science
      and Health, B15(5), 519-528 (1980).

-------
                                                             Section No. 3.16.1
                                                             Date June 30.  1988
                                                             Page 4


38.  VOC  Sampling  and Analysis Workshop,   Volume  III.    U.   S.  Environmental
     Protection Agency Publication No. EPA-340/1-84-001C,  September 1984.

39.  Knoll, J.  E.,  M. A.  Smith, and M. R.  Midgett.   Evaluation of Emission Test
     Methods  for   Halogenated  Hydrocarbons,   Volume  I.    U.   S. Environmental
     Protection Agency Publication No. EPA-600/4-79~025, March  1979.

40.  Binetti, R. et al.  Headspace Gas  Chromatographic Detection  of  Ethylene
     Oxide in Air.  Chromatographia, Vol. 21,  December 1986.

111.  Butadiene, Method  591.   NIOSH  Manual of Analytical Methods,  Volume  2,
     Second Edition, U. S. Department of Health and Human  Services, April  1977.

42.  Knoll,  J. E.  Estimation of the Limit  of  Detection  in Chromatography.
     Journal of Chromatographic Science, Vol.  23, September 1985.

43.  Procedure  1  - Determination of Adequate Chromatographic  Peak  Resolution.
     Code of Federal Regulations, Title 40. Part 6l. Appendix C, July 1, 1987-

44.  Method 625 -  Base/Neutrals and Acids.  Code of Federal Regulations,  Title
     40. Part 136. Appendix A, July 1, 1987.

45.  C. through C_ Hydrocarbons in the Atmosphere by Gas Chromatography.   ASTM I/   J
     2820-72,  Part  23.   American   Society   for   Testing   and   Materials, ^—/
     Philadelphia, PA, 23:950-958, 1973.

46.  Corazon,  V.   V.   Methodology for Collecting  and Analyzing  Organic  Air
     Pollutants.    U.   S.  Environmental  Protection Agency   Publication  No.
     EPA-600/2-79-042, February 1979.

47.  Dravnieks, A.,  B.  K.  Krotoszynski, J. Whitfield,  A.  O'Donnell,  and  T.
     Burgwald.   Environmental Science and Technology, 5(12):1200-1222, 1971.

48.  Eggertsen, F. T., and F. M. Nelson.  Gas Chromatographic Analysis of  Engine
     Exhaust and Atmosphere.  Analytical Chemistry,  30(6):  1040-1043, 1958.

49.  Feairheller,   W. R.,  P. J. Marn, D. H. Harris,  and D.  L. Harris.  Te<3inical
     Manual  for  Process  Sampling  Strategies for Organic  Materials,    U.  S.
     Environmental Protection Agency, Publication  No. EPA  600/2-76-122.  April
     1976.

50.  FR, 39 FR 9319-9323,  1974.

51.  FR. 39 FR 32857-32860. 1974.

52.  FR, 41 FR 23069-23072 and 23076-23090, 1976.

53.  FR, 41 FR 46569-46571, 1976.

54.  FR, 42 FR 41771-41776, 1977.

-------
                                                             Section No.  3.16.11
                                                             Date June 30,  1988
                                                             Page 5

55.  Fishbein, L.  Chromatography  of Environmental Hazards,  Volume II. Elsevier
     Scientific Publishing Company, New York, New York, 1973-

56.  Hamersma, J. W., S. L. Reynolds, and R. F.  Maddalone.    EPA/IERL Procedures
     Manual:  Level  1 Environmental Assessment, U. S. Environmental  Protection
     Agency Publication No. EPA 600/276/l60a, June 1976.

57.  Harris,  J.  C.,  M.  J.  Hayes, P. L. Levins, and D.  B. Lindsay.  EPA/IERL
     Procedures for Level  2  Sampling and Analysis of Organic Materials.  U. S.
     Environmental Protection Agency Publication No. EPA 600/7-79-033,  February
     1979-

58.  Harris, W. E.,  H.  W. Habgood.  Programmed Temperature Gas Chromatography.
     John Wiley & Sons, Inc.  New York,  1966.

59•  Methods  of Air Sampling and Analysis.   Intersociety  Committee,  American
     Health Association, Washington, D. C., 1972.

60.  Jones,  P.  W.,  R.   D.   Grammer,  P.  E.  Strup,  and  T.  B.  Stanford.
     Environmental Science and Technology, 10:806-810, 1976.

61.  McNair Han Bunelli, E. J. Basic Gas Chromatography.  Consolidated Printers,
     Berkeley, 1969.

62.  Nelson, G. 0. Controlled Test Atmospheres,  Principles and Techniques.    Ann
     Arbor, Ann Arbor Science Publishers, 1971.

63.  Schuetzle, D., T. J. Prater, and S. R. Ruddell.  Sampling and  Analysis  of
     Emissions  from  Stationary  Sources;  I.   Odor  and  Total  Hydrocarbons.
     Journal of the Air Pollution Control Association, 1975-

64.  Snyder,  A.  D., F. N. Hodgson, M. A. Kemmer, and J. R.  HcKendree.  Utility
     of Solid Sorbents  for  Sampling Organic Emissions from Stationary Sources.
     U. S. Environmental  Protection  Agency  Publication  No. EPA 600/2-76-201,
     July 1976.

65.  Tentative  Method  for  Continuous  Analysis of Total Hydrocarbons  in  the
     Atmosphere.  Intersociety  Committee,  American  Public Health Association,
     Washington, D.C., 1972.

66.  Zwerg, G.  CRC Handbook of Chromatography,  Volumes  I  and  II.  CRC Press,
     Cleveland, 1972.

-------
o
o
o

-------
                                                                Section No. 3.16.12
                                                                Date June 30, 1988
                                                                Page 1
12.0   DATA FORMS

      Blank data forms  are provided on the following pages for the  convenience  of
 the Handbook user.  Each blank  form has the custoaary descriptive title centered  at
 the top of the page.  However,  the  section-page documentation in the top right-hand
 corner of each page has been replaced with a number in the lower right-hand corner
 that will enable the user to identify and refer to a similar filled-in  fora  in a
 text section.   For example,  form M18-2.5  indicates that the form is Figure 2.5  in
 Section $.18.2 of  the Method 18 section.   Future revisions of these forms, if  any.
 can be documented by  2.5a, 2.5b, etc.  Nineteen of the blank forms listed below are
 included in this section.  Six have been left blank in the text as shown following
 the form number.
 Form
      Title

Flowmeter Calibration Data Form
(English and metric units)

Critical Orifice Calibration Data Form
(English and metric units)

Dynamic Dilution Data Form

Static Dilution Data Form

Thermometer Calibration Forn

Preliminary Survey Data Sheet

Preliminary Survey Preparations

Pretest Sampling Checks

Pretest Preparations

Field Sampling Data Form for Container Sampling

Field Sampling Data Form for Direct Interface Sampling

Field Sampling Data Form for Adsorption Tube  Sampling

On-site Measurements Checklist

Data Form for Analysis of Method 18 Samples

Calibration Standard Preparation Data Form for Diluted
Gas Cylinders

Calibration Data Form for Preparation of Standards in
Tedlar Bags by Gas and Liquid Injection

-------
                                                                Section No.  3.16.12
                                                                Date June 30, 1988
                                                                Page 2
o
5.8                    Data Form for Development of Response and Relative
                       Retention Factors

5.9                    Data Form for Preparation of Liquid Standards and
                       Desorption Efficiency Samples for Adsorption Tube Analysis
5.10 (Text)            Postsampling Operations Checklist

6.1                    Calculation Form for GO Analysis by Gas Injection

6.2                    Calculation Form for GC Analysis by Liquid Injection

8.1                    Field Audit Report Form

8.2                    Method 18 Checklist to be Used by Auditors
                                                                            O
                                                                            o

-------
                 FLOWMETER CALIBRATION DATA FO
                                       glish units)
Date
     Calibrated by
Meter system no.
Barometric pressure, Pm =	
Type of primary meter:  wet test	
Type of flowmeter calibrated:  rotameter
                          in. Hg   Ambient temperature
Primary meter no.
        op
                             ,  dry gas
                     , or bubble meter
                                  , dry gas meter
                          or mass flowtneter
Primary meter readings
Initial
reading
(vpl),»
ft3



Final
reading
(V),'
ft3



Initial
temp,°F
(tpi)
op



Final
temp,°F
(tpr>
oF



Press
drop
(Dp)<
in.
H20



Flowmeter readings
Initial
reading

-------
                             FLOWMETER CALIBRATION DATA FORM (metric units)
Date
                  Calibrated by
Meter systen no.
Primary deter no.
        °C
Barometric pressure, Pn * 	  mn Hg  Ambient temperature 	
Type of primary meter: wet test 	, dry gas 	, or bubble meter
Type of flowmeter calibrated: rotaineter
                                              ,  dry gas meter
                       ,  or mass flowmeter
Primary meter readings
Initial
reading
(vpi).a
m3



Final
reading
(vpf),a
D3



Initial
temp,°F
('PI*
°C



Final
temp,°F
(tpf)
°C



Pres
drop
(V
mm
^0



Flowmeter readings
Initial
reading
(V,i).b
Ej3 or
ia- /nin



Final
reading
(V"
n3 or
ia3/min



Initial
temp
(t.i)
°C



Final
temp

°C



Press
drop
(Ds).c
mm
H20



Time
min
(9)td
min



Calibration
factors
(Yt).e



(Y)



tt  Volume passing through the neter using the initial  and final readings and requires a minimum of at
   least five revolutions of the meter.
b  Volume passing through the meter using the initial  and final readings or the indicated flow rate
   using the initial and final flow rate setting.
0  Pressure drop through the meter used to calculate the neter pressure.
d  The time it takes to complete the calibration run.
e  With Y defined as the average ratio of volumes  for  the primary meter compared to the flowmeter
   calibrated, Yj = Y + 0.03Y for the calibration  and  Yj = Y + 0.05Y for the posttest checks;  thus,

   For calibration of the dry gas neter:
          - Vpiint.i * fc.f)/2 *'273°K][P.  * {Dp/13.6)]                _ YI
                                  273"K][P.

    For calibration of the rotaneter and nass flowaeter:

                        fc.f)/2 * 273°K][PB
                                                                                            (Eq. 2-6)
                                             (Dp/13.6)]
o
                             tpf)/2 + 2738K][Pa
                                                          {Eq.  2-7),  Y -
                                                                                            (Eq.  2-8)
                                                  o
                         Quality Assurance Handbook H18
                          -O

-------
                            CRITICAL ORIFICE CALIBRATION DATA FORM (English units)
Date
             Calibrated by
Meter system no.
Primary meter no.
       op
Barometric pressure, Pa = 	 in. Hg  Ambient temperature
Type of primary meter: wet test 	, dry gas 	, or bubble meter
Type of critical orifice: capillary glass
                                               needle or tubing
                                ,  or adjustable
Primary meter readings
Initial
reading
(Vpi)/
ft3



Final
reading
(vpf),a
ft3



Initial
temp,°F

-------
                                 CRITICAL ORIFICE CALIBRATION DATA FORM (metric  units)
       Date
Calibrated by
                                          Meter system no.
       Barometric  pressure,  PB  = 	
       Type of primary meter: wet test 	
       Type of critical orifice: capillary glass
Primary neter no.
        °C
                     mm Hg    Ambient temperature 	
                     	, dry gas 	, or bubble meter
                                  needle or tubing
                                                                          ,  or adjustable
Primary meter readings
Initial
reading

mm
H20



Critical orifice readings
Initial
setting
b
L or
L/min



Final
setting
b
L or
L/min



Press
drop
c
mm
Hg



Time
rain
(9),"
min



Calculated
flow rate
W(.td)]'
L/min



Calibration
factor'
(K'J



(K')



        *   Volume passirig through the meter using the initial and final readings and requires a minimum of at
           least five revolutions of the meter.
        b   Volume passing through the orifice using the initial and final readings  or the  indicated flow rate
           using the initial and final flow rate setting (for variable setting orifice only).
        c   Pressure drop through the meter used to calculate the meter pressure.
        d   The time it takes to complete the calibration run.
        e   With K'  defined as the average orifice calibration factor based on the volumes  of the primary test
           meter, K't  = K1.^ 0.03K1  for the calibration and K'j * K1  + 0.05K1  for the posttest checks; thus,
           Flow rate of the primary meter at standard conditions:

                      0.3858(Vpf  - Vpl)(P0 + Dp/13.6)
               td)
                                 tf)/2 * 2?3°C]
                            (Eq. 2-13), Q(ltd) =
                                  pf
                                                     0
                                                                                                   (Eq. 2-
For determination of the K1 for the critical orifice:


                                     	 (Eq. 2-15), &
                                                                              K'
                                                          K'
                                                                                                    (Eq. 2-16)
                             • ba r
                                   e
o
                          o
                                                                            Quality Assurance Handbook Ml2-«2.2B

-------
                            DYNAMIC CALIBRATION DATA FORM
 Date 	
 Source flovnaeter number	
 Stage 1 flowoeter number	
 Stage 2 flovnaeter number 	
 Barometric press 	mm (in.) Hg
 Organic compound 	
                  Calibrated by 	
                  Date source meter calibrated _
                  Date stage 1 meter calibrated
                  Date stage 2 meter calibrated
                  Heated box temperature 	
                  Leak check for total system
 Certified concentration
         ppmv(X)  Date of calibration curve
 STAGE 1
 Emission gas flowmeter reading, ml/min  (q,.,).
 Diluent gas flovnaeter reading, ml/min
 Dilution ratio
 Injection time, 24h
 Distance to peak, cm
 Chart speed, cm/min
 Retention time, min
 Attenuation factor
 Peak area or units
 Peak area X attenuation factor
 Measured concentration,* ppmv
 Calculated concentration," ppmv (C, )
 Percent difference,6 %         ,
                          RUN 1
RUN 2
 STAGE 2 (if applicable)
 Emission gas flovnaeter reading, ml/min
 Diluent gas flowsaeter reading, ml/min
 Dilution ratio
 Injection tins, 24h
 Distance to peak, cm
 Chart speed, cm/min
 Retention time, min
 Attenuation factor
 Peak area or units
 Peak area X attenuation factor
 Measured concentration,' ppmv
 Calculated concentration,4 ppmv
 Percent difference,6 %
                          RUN 1
RUN2
RUN3
v * See Figure 5-1 for calculation.
        106 x (X x qc )
 c Percent Difference
3 Calculated concentration for single stage

 Calculated Concentration- - Measured Concentration

              Measured Concentration
            x 100J5
   C. = 106 x X
                           = Calculated cone, for two stage
                                                   Quality Assurance Handbook M18-2.5

-------
Date
Source flowneter number
Dry gas meter number
Ambient temperature
Barometric press _
Organic compound
Certified concen,
                             STATIC DILUTION DATA FORM
                                        Calibrated by
                                                                                 o
                            °C (°F)
                        mm (in.) Hg
(X)
                               ppmv
                                        Date source meter calibrated _
                                        Date dry gas meter calibrated
                                        Dry gas meter calib factor (Y)
                                        Leak check for total system _
                                        Vacuum during leak check  _ _
                                        Date of calibration curve
Initial dry gas meter reading, L (ft3)
Final dry gas meter reading, L (ft3)
Volume of diluent gas metered, L (ft3)
Gas metered X calibration factor (Y),{V2}
Flowmeter sampling rate, ml/min (cfm)
Sampling time, nin
Sampling rate X sample tine , L ( ft3 ) , { Vt }
Dilution ratio
Injection time, 24h
Distance to peak, en
Chart speed, en/rain
Retention time, nin
Attenuation factor            •
Peak area or units
Peak area X attenuation factor
Measured concentration,* ppmv
Calculated concentration,11 pprav, {Cs}
Percent difference,* %
                                                RUN 1
                                                             RUN 2
*  See Figure 5»i for calculations.

b  Calculated concentration (C,) **
                                              V2)
                                                                      ppmv
c  Percent difference, #d
                             Measured concent - Calculated concent
                                     Measured concentration
                                                                    X 100
   The percent difference must be less than 10 % absolute.
                                                 Quality Assurance Handbook H18-2.6
                                                                                   O

-------
                                  THERMOMETER CALIBRATION FORM
Date








Reference
thermometer
type








Calibi
thermc
type








•ated
>meter
use








no.








Ambler
refer*








it temper
calibrb








Meaaurec
*ature
differc








[ values
Bo:
refer*








i
iling wal
calibrb








;er
differc








Calibrator's
initials








Temperature reading of the reference thermometer in °C or °F.
Temperature reading of the thermometer being calibrated in °C  or °F.
Difference between the reference thermometer and the calibrated thermometer.   This difference must
be less than 3°C (5.4°F) for than initial calibration and 6°C  (10.4°F)  for the calibration check.
                                                                  Quality Assurance Handbook M18-2.7

-------
                               FIELD SAMPLING DATA FORM FOR CONTAINER SAMPLING
   Plant 	
   City  	
   Operator
   Date
Flowneter calib.(Y)
Container type:  bag
   Run number	
   Stack dia, mm (in.)
   Sample box number
                syringe
                canister
Container volume,  	
Container number 	
Average ( P)  	
Initial flowmeter  setting
Average stack temp
         Dilution system:  (dynamic)
          emission flowsetting 	
          diluent flowsetting 	
	  Dilution system:  (static)
 liters   emission flowsetting
         Final leak check
m3/min (cfra)
                                                         mm (in.) IljO  Vacuum during leak check
   Pitot tube (Cp) 	
   Static press 	 mm (in.) HjO  Barometric press
°C (°F)  Sampling point location
                              mm  (in.) H20
                       mm (in.) Hg
Sampling
time,
tain






Total
Clock
time,
2k h







Velocity head
mm (in.) H.,0,
. ( P)






Avg
Flowineter
setting
L/min (ft3/min)






Avg
stack -
°C (°F)






Avg
probe
°C (°F)






Avg
Temperature
sample line
°C (°F)






Avg
readings
flbwmeter box
°C (°F)





;
Avg
container
°C (°F)






Avg
o
                o
       Quality Assurance Handbook Ml8
      -o

-------
                        FIELD SAMPLING DATA FORM FOR DIRECT INTERFACE SAMPLING
Plant 	
City  	
Operator
Date
                                Barometric press  	
                                Initial probe setting
                                Sampling rate 	
                        mm (in.) Hg
                            °C (°F
                                Sampling point location
              Sample loop volume
              Sample loop temp 	
L/min (cfm)   Column temperature:
                               ml
Run number 	
Stack dia, mm (in.)
Meter box number
Stack temp 	
Static press 	
                  mm (in.)
Dilution system:
 source flow rate
 diluent flow rate
 diluent flow rate
Dilution ratio
                                                        L/min (cfm)
                                                        L/min (cfm)
                                                        L/min (cfm)
initial /
program rate
final /
Carrier gas flow

/


°C/min
°C/min
°C/min
ml/min
Dilution system check
Final leak check 	
Vacuum § check
                                  mm (in.) H20
Time of
injection
24 h







Injection
number







Flo*
source
ml/min







nneter(s) s
diluent
ml/min







ettings
diluent
ml/min







stack
°C (°F)







Temperal
probe
°C (°F)







;ure readings
sample line
°C (°F)







injection port
°C (°F)







                                                                     Quality Assurance Handbook M18-4.2

-------
                           FIELD SAMPLING DATA FORM FOR ADSORPTION TUBE SAMPLING
  Plant 	
  City  	
  Operator
  Date
  Run number 	
  Stack dia, mm (in.)
              Flowmeter calib.(Y) _
              Adsorption tube type:
               charcoal tube  	
               silica gel 	
               other
             Dilution system: (dynamic)
              emission flowsetting 	
              diluent flowsetting
             Dilution system: (static)
              emission flowsetting 	
             Final leak check
  Meter box number
  Pitot tube (Cp)  _
  Static press 	
              Adsorption tube number 	
              Average ( P) 	mm (in.) H20  Vacuum during leak check
m3/min (cfm)
              Initial flowineter setting
              Average stack temp
                                   mm (in.) H.O
mm (in.) H20  Barometric press
    'C (°F)  Sampling point location
nm (in.) Hg
Sampling
time,
min






Total
Clock
time,
24 h







Velocity head
mm (in.) H.O,
( P)






Avg
Flowmeter
setting
L/min (ft3/min)






Avg
stack
°C (°F)






Avg
Temperature i
probe, line
°C (°F)






Avg
'eadings
adsorp. tube
°C (°F)






Avg
meter
°C (°F)






Avg
Vacuum
mm (in.) Hg






Avg
o
                                o
             Quality Assurance Handbook MlS-^

-------
                        ANALYSIS OF METHOD 18 FIELD SAMPLES
Date: 	
Location:
                  Analyst:
	  Plant:
 Sample Type:
Type of Calibration Standard: 	
Number of Standards: 	  Date Prepared:
                                             Target Compound:
                                                     Prepared By:
GC Used: 	
Carrier Gas Used: 	•
Column Temperatures, Initial:
Sample Loop Volume:
Detector Temp.:  	
                            Column Used:
                                 Carrier Gas Flow Rate:
                                 	  Program Rate: 	
                     	  Loop Temperature:
                     Auxiliary Gases: 	
                 	  Final:
           Inject. Port  Temp.:
Calibration Data                   Standard 1
 First analysis/second analysis
  Standard concentration (Cact)    	
  Flow rate through loop (ml/min)      /	
  Liquid injection volume (tubes)      /	
  Injection time (24-hr clock)         /
  Chart speed (cm/min)                 /	
  Detector attenuation                 /	
  Peak retention time (oin)             /	
  Peak retention time range (min)	
  Peak area                            /	
  Peak area x attenuation factor       /	
  Average peak area value (Y)       	
  Percent deviation from average   	
  Calculated concentration (Cstd)  	
  % deviation from actual (#Dact)	
  Linear regression equation;  slope (m): 	
                                                  Standard 2
                          Standard 3
                                                  y-intercept (b):
Sample Analysis Data
 First analysis/second analysis
  Sample identification
  Interface dilution factor
  Flow rate through loop (ml/min)
  Liquid injection volume (tubes)
  Injection time (24-hr clock)
  Chart speed (cm/min)
  Detector attenuation
  Peak retention time (min)
  Peak retention time range (min)
  Peak area
  Peak area x at ten.  factor (AJ/A
  Average peak area value (Y)
  % deviation from average (%D
  Calculated concentration (C )
Sample 1
                                                   Sample 2
                           Sample 3
                                g
                                 )
' (Y -
/•» I-IT-'P -
^-std Or °s 	
m
b) '

*VV8 =
-A, - Y
Y
v mot 2n -
x ±uu^ ^ua c t -
td ~ Cact
Y
x 100?
                                                Quality Assurance Handbook M18-5.1

-------
           PREPARATION OF STANDARDS  BY DILUTION OF GAS CYLINDER STANDARDS
                                                                              o
Date: 	  Preparer:  	  Purpose:
Cylinder Component:	  Source:
Component Concentration (X-):  	 ppm   Certification Date:
          Stage 1                        Mixture 1      Mixture 2      Mixture 3
     Standard gas  flowmeter reading     	      	      	
     Diluent gas flowmeter reading      	      	      	
     Laboratory temperature ,(°K)         	      	      	
     Barometric pressure (Pb)  (mm Hg)   	      	      	
     Flow rate  of cylinder gas (qcl) at
       standard conditions (ml/min)     	      	      	
     Flow rate of  diluent gas   (
-------
       PREPARATION OF STANDARDS  IN TEDLAR BAGS BY GAS AND LIQUID INJECTION
Date:
                Preparer:
                                            Purpose:
Organic Compound:
Compound Source:
                                                      Gas:
                                                                 or Liquid:
                       Compound Purity (P) :
                                                % Compound Mole Weight (M):
      Gas Injection                   Mixture 1      Mixture 2      'Mixture 3
Bag number or identification          _      _. _      _ _
Dry gas meter calibration factor  (Y)  _         . _      _ ••
Final gas meter reading, liters       _      _      ,
Initial gas meter reading, liters          •          _      _
Volume metered (VB), liters           _______      _      _
Ambient temperature, °C               _ _      _      _
Average gas meter temperature, °C     _      _      _
Absolute gas meter temp. (T0), °K     _      _      ________
Barometric pressure  (Pb), mm Hg           ' _      _ _____      _
Average gas meter pressure, mm Hg     _      _ _      _
Absolute gas meter press. (PB). mm Hg _      _      _
Gas volume injected  (Gv ) , ml          _      _          . _
Syringe temperature  (T_ ) , °K          _      ____ _      _
Absolute syringe pressure (P } , mm Hg _      _      _
Calculated concentration (C.)         _        _      _
                           O t            mm~—~^—^      -               ««^^— i i !• ......
       GV x 103 x
                  P. x TB
                                                           . calc
                                                 . corr
                                                                     100*
            Vp x Y
    Liquid Injection                  Mixture 1      Mixture 2      Mixture 3
Bag number or identification          _ ___      _      _
Dry gas meter calibration factor (Y)  _      _      _
Final gas meter reading- liters       _      _      _
Initial gas meter reading, liters     _      _      _
Volume metered (VB ) , liters           _      _      _ _
Average gas meter temperature, °C     _      _      _
Absolute gas meter temp. (TB), °K     _      _      _
Barometric pressure (Pb ) , mm Hg           ••          _         ' _
Average gas meter pressure, mn Hg     _      _      _
Absolute gas meter press. (PB)t mm Hg    _      _ __     .    _
Liquid organic density (p) , ug/ml     _      _      _
Liquid volume injected (Lv ) , ttl       _      _ __^__      __ _
Calculated concentration (C_ )              •          _      _
      ,  ,      „
C   = 6.24 x 104  x
                   M x V0 x Y x P0
                                                 8  corp
                                                                     100%
                                               Quality Assurance Handbook H18-5-6

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      DEVELOPMENT OF RELATIVE RESPONSE FACTORS AND RELATIVE RETENTION FACTORS
                                                                              o
Date: 	
Target Compound: 	
Surrogate Compound:
Preparer:
                                    	  Purpose:
                                     Type of Standard:
                                     Type of Standard:
Target Compound Calibration Data        Standard 1
 First analysis/verify analysis
    Standard concentration              	
    Flow rate through loop (ml/min)         /	
    Liquid injection volume (tubes)         /	
    Injection time (24-hr clock)            /	
    Chart speed (cm/min)                    /	
    Detector attenuation                    /	
    Peak retention time (tRxl/tRxf)         /	
    Peak retention time range           	
    Peak area                               /	
    Peak area x atten. factor (Y1/YX)       /	
    Verification analysis conc.(Cx)     	
    Percent deviation from actual       	
    Caculated retention time (rTxf)     	
    Percent deviation from actual       	
Linear regression equation;   slope (m_): 	
                                                       Standard 2
                                                    Standard 3
                                                   y- intercept (b) :
                                                                              O
Surrogate Calibration Data
 First analysis/second analysis
    Standard concentration
    Flow rate through loop (ml/min)
    Liquid injection volume (tubes)
    Injection time (24-hr clock)
    Chart speed (cm/mni)
    Detector attenuation
    Peak retention time (tRsl/tRg.r)
    Peak retention time range
    Peak area
    Peak area x attenuation factor
Linear regression equation; slope (ms)
                                        Standard 1
                                     Standard 2     Standard
                                                (mf):.
                                          y-intercept (b):
Nonretained peak retention time (tM1/tMf):
Relative Response Factor (F_ ):
                      Relative Retention Factor (rx/s):
         m_
                      Lx/.
           (tRsi - tM1)
                                                           x F,
                                            Rx
                                                       s td
                                                                              O
                                                 Quality Assurance Handbook M18-5-8

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  DATA FORM FOR PREPARATION OF LIQUID STANDARDS AND DESORPTION EFFICIENCY SAMPLES
Date:
                Preparer:
Purpose:
Organic Compound:  _
Compound Source: 	
Adsorbent Material:
                                                      Gas:
                     or Liquid:
                       Compound Purity (P):
                                 Batch No:
   Jt Compound Mole Weight (M):
       Desorption Solvent: 	
  Standards in Solvent
                                      Mixture 1
         Mixture 2
                                  ml
Mixture 3
Desorption solvent volume (V,),
Compound spike amount (V0),  ul
Organic compound density (p), ug/ul
Standard concentration (Cg), ug/ml
  Standards on Adsorbent
  Adsorbent amount,  g
  Compound spike  amount (V0),  ul
  Organic compound density (p),  ug/ul
  Desorption solvent volume  (Ve),  ml
  Desorption time, min
  Standard concentration (CB), ug/ml
                                    Mixture 1   Mixture 2   Mixture 3  Blank
  GC Operating Conditions
  Injection port  temperature,  °C
  Carrier gas  flow  rate,  ml/min
  Column temperature:
       Initial, °C
       Program rate, °C/min
       Final,  °C
  Chromatographic Results
  Injection time, 24-hr clock
  Distance to peak,  cm
  Chart speed,  cm/min
  Retention time, min
  Attenuation factor
  Standards in  desorption solvent:
       Peak area  (Ae),  area counts
  Standards and blank from
    adsorbent material:
       Peak area  (AB  and
          area  counts
                                    Mixture 1   Mixture 2   Mixture 3  Blank
  Desorption Efficiency Calculation     Mixture 1    Mixture 2    Mixture 3
  Desorption Efficiency (DE),  %         	    	    	
       Vo  x p x P

       Vs  x 1002
                                         DE
                                              A. -
          x 100*
                                                 Quality Assurance Handbook M18-5-9

-------
                 CALCULATION FORM FOR GC ANALYSIS BY GAS INJECTION
                                                                              o
                                SAMPLE CONCENTRATION

CB  =	ppm,   Pr  =	. 	  on Hg,   T±  =	. 	  °K,

Pi  =	. _  mm Hg,   Tr  =	. _  °K,   BM8  =  0  .	,

K*  =  0 .,   F    =
             C. Pr Tt Fr K
     Cc  =  -  =  ___ ppm                     Equation  6-1
            PI Tr (1 - BW.K)
'If applicable.
                                                                              O
                                                 Quality Assurance Handbook Ml
o

-------
                CALCULATION FORM FOR GC ANALYSIS BY LIQUID INJECTION
                  SAMPLE VOLUME, DRY BASIS AT STANDARD CONDITIONS
V0
      =	._  °K.   Bw/   =  0.	.   K'  =  0.	



                              P    V
                               bar   o
     V.ta.dry  s  0.3858  	  =	L       ~  Equation 6-2
                                  - B
                                     w.
"If applicable.




                               DESORPTION EFFICIENCY


Qr=	,   Qtt=	,   B  =	




     DE  =  (Q,. - B)/Qa  =  o .	                                Equation 6-3
                                SAMPLE CONCENTRATION


Wp  =	ug,   Wb  =	ug,   Bp  =	ug.


Bb  =	ug,   V.td  =	. 	 L,  DE  =  0.	.


K'  =  0 .
            
-------
                            FIELD  AUDIT REPORT

Part A. - To be filled out by organization supplying audit cylinders.
          1. Organization supplying audit sample(s)  and shipping address

          2. Audit supervisor, organization,  and phone number

          3. Shipping instructions: Name, Address, Attention
                                                                  o
5.
6.
             Guaranteed arrival date for cylinders -
             Planned shipping date for cylinders -
             Details on audit cylinders from last analysis




d. Audit gas (es) /balance gas..



Low cone.







High cone







Part B. - To be filled out by audit supervisor.
          1. Process sampled -	
             Audit location
2.
3.
Name of individual audit
Audit date
5. Audit Results:
                                                                            O




d. Measured concentration, ppm
e. Actual audit concentration, ppm
f. Audit accuracy:1

Percent1 accuracy =
Measured Cone. - Actual Cone. x 100
Actual Cone.

Low
cone.
cylinder









High
cone.
cylinder









       1 Results of two consecutive injections  that meet  the sanple analysis
        criteria of the test method.
                                           Quality Assurance Handbook Ml8-£

-------
                           METHOD 18 AUDIT CHECKLIST
Yes
No
Comments
Operation
                                       PRESAMPLING PREPARATION
                           1.  Knowledge of process operations
                           2.  Results of pretest audit (+_ 10% or other value)
                           3.  Calibration of pertinent equipment, in
                               particular, dry gas meters and other flowmeters
                           4.  Selection and checkout of equipment for proper
                               sampling and analytical techniques
                               BAGS - reactivity,  condensation, & retention
                               ADSORPTION TUBES - adsorption & desorption
                                                  efficiency
                               DILUTION SYSTEM - dilution ratio
                               GC/COLUMN - adequate resolution
                               GC/DETECTOR - acceptable accuracy & precision
                                        ON-SITE MEASUREMENTS
                           5-   Results of on-site audit (+_ 10% or other value)
                           6.   Sampling system properly assembled
                           7.   Based on pi tot tube check,  is proportional
                               sampling required (more  than 10% flow change)
                           8'.   Dilution system check acceptable (if applicable)
                           9.   Sampling system leak check acceptable
                          10.   Proportional  sampling properly conducted
                          11.   Constant rate sampling properly conducted
                          12.   Heater systems maintained at proper temperatures
                          13.   Proper number of samples & sampling time
                          14.   GC properly calibrated
                          15.   Duplicate injections had acceptable precision
                          16.   Recording of  pertinent process conditions during
                               sample collection,  samples  properly identified,
                               and calculations properly conducted
                                          POSTSAMPLING
                          17.  Results of off-site audit  (+, 10% or other value)
                          18.  GC properly calibrated
                          19.  Duplicate injections had acceptable precision <5%
                          20.  Adsorption efficiency acceptable,>9Q% on  primary
                          21.  Desorption efficiency accept able,>50% recovery
                          22.  Adequate peak resolution
                          23.  Bags passed reaction check,  less than 10% change
                          24.  Bags passed retention check,less than 5#  retained
                          25.  Flowmeters recalibration acceptable
                          26.  Temperature sensor recalibration acceptable
                                             COMMENTS
                                             Quality Assurance Handbook M18-8.2

-------
o
o
o

-------
                                                            Section  No.  3.1?
                                                            Date May 31,  1991
                                                            Page 1
                                    Section 3.1?
      METHOD 25 - DETERMINATION OF TOTAL GASEOUS NONMETHANE ORGANIC  EMISSIONS
                         AS CARBON FROM STATIONARY SOURCES
                                      OUTLINE
      Section

SUMMARY
  \
METHOD HIGHLIGHTS

METHOD DESCRIPTION

     1.
PROCUREMENT OF APPARATUS
AND SUPPLIES
     2.   CALIBRATION OF APPARATUS

     3.   PRESAMPLING OPERATIONS

     4.   ON-SITE MEASUREMENTS

     5.   POSTSAMPLING OPERATIONS

     6.   CALCULATIONS

     7.   MAINTENANCE

     8.   AUDITING PROCEDURES

     9.   RECOMMENDED STANDARDS FOR
          ESTABLISHING TRACEABILITY

     10.   REFERENCE METHODS

     11.   REFERENCES
Documentation
3.17
3-17
3.17.1
3.17.2
3.17-3
3.17.4
3.17.5
3-17.6
3.17.7
3-17.8
3.17.9
3.17.10
3-17.11
Number
of Pages
2
3
25
9
9
14
30
11
2
9
1
25
°1

-------
                                                            Section No.  3.1?
                                                            Date Hay 31.  1991
                                                            Page 2
o
                                        SUMMARY
      Method 25 applies  to  the measurement of volatile organic compounds  (VOC)  as
total gaseous nonmethane  organics  (TGNMO)  as carbon in source emissions.   Organic
particulate matter will  interfere  with the analysis and, therefore,  a  particulate
filter is required.  The  minimum detectable  concentration for the method is 50 ppm
as carbon.
     When carbon dioxide  (C02)  and water vapor are present together  in the stack,
they can produce a positive bias in the  sample.  The magnitude of the bias depends
on the  concentrations  of C02  and  water  vapor.  As a  guideline,  multiply  the C02
concentration  times  the  water vapor  concentration,  both  expressed  as  volume
percent.    If  this  product  does   not  exceed 100,  the bias  can  be considered
insignificant.    For example,   the  bias  is  not significant  for  source emissions
containing 10 percent C02  and  10. percent water vapor,  but it would  be  significant
for a source with VOC emissions ( near  the  detection limit and with  10  percent C02
and 20 percent water vapor.
     An emission  sample  is withdrawn  from the stack  at a constant  rate through a
heated filter and  a  chilled condensate trap by means of  an evacuated sample tank.
After sampling  is completed,  the  TGNMO  are determined by independently analyzing
the condensate trap and sample tank fractions and combining the analytical  results.
The organic content of the  condensate  trap fraction is  determined by oxidizing the
NMO to C02 and quantitatively  collecting the effluent in an evacuated vessel; then
a portion of the C02 is  reduced to CH^, and measured by  a flame ionization  detector  x*~"\
(FID).  The organic content  of the sample  tank fraction is measured by  injecting af   J
portion of  the  sample  into a  gas  chromatographic  column to separate the  NMO fromV—'
carbon monoxide  (CO),  C02,  and CH^; the NMO are oxidized to C02, reduced to CHft,
and  measured by   an  FID.   In this  manner,  the variable  response  of   the FID
associated with different types of organics is eliminated.
     This method  is not  the only method that  applies to  the  measurement of TGNMO.
Costs, logistics,  and  other practicalities  of source  testing may make other test
methods  more desirable  for measuring VOC contents of certain effluent  streams.
Proper  judgment  is required  in determining  the most  applicable  VOC test method.
For example, depending upon the molecular weight  of  the organics in the  effluent
stream,  a  totally automated   semicontinuous:; nonmethane organics   (NMO)  analyzer
interfaced directly  to the source may yield accurate  results.  This approach has
the advantage  of  providing  emission   data semicontinuously over  an  extended time
period.
     Direct measurement of an effluent with an FID analyzer may be appropriate with
prior characterization of the gas  stream  and  knowledge  that  the  detector  responds
predictably  to  the organic  compounds  in  the stream.   'If present,  methane  (CHA)
will,  of course, also be  measured.  The  FID can be applied to the determination of
the mass  concentration of the  total molecular structure of  the  organic  emissions
under any of the following limited conditions: (1)  where only  one  compound  is known
to exist;  (2) when the organic compounds  consist  of only hydrogen  and  carbon; (3)
where the relative percentages of the  compounds are known or can be determined, and
the FID responses to the compounds are known;  (^) where a consistent mixture of the
compounds  exists  before  and after  emission control  and only  the   relative
concentrations are to be  assessed;  or  (5) where the FID  can  be calibrated against
mass standards of the compounds emitted  (solvent emissions,  for example).
     Another example of direct use of an FID is as  a screening method.  If  there is
enough information available  to provide  a rough estimate of its accuracy, the FID
analyzer can be used to determine the VOC content of an uncharacterized gas stream.
 O

-------
                                                            Section No.  3.1?
                                                            Date May 31,  1991
                                                            Page 3

With a sufficient buffer to account for possible inaccuracies,  direct use of an FID
can  be a  useful tool  to  obtain  the  desired  measurements without costly  exact
determination.    In  situations  where  qualitative/quantitative  analysis of  an
effluent stream is desired or required, a gas chromatographic FID system may apply.
However, for  sources emitting numerous  organics,  the  time and  expense of  this
approach will be formidable.

-------
                                                            Section No.  3.17
                                                            Date May 31,  1991
                                                            Page 4
o
                            METHOD  HIGHLIGHTS
     Section  3.17  describes  the  procedures  and specifications  for  determining
volatile  organic compounds  as total gaseous  nonmethane  organics from  stationary
sources.    An emission  sample is  withdrawn  from  the stack  at  a  constant  rate
through  a heated filter  and  a chilled  condensate  trap by  means of an  evacuated
sample  tank.    After  sampling   is  completed,  the TGNMO   are determined by
independently analyzing the condensate trap and sample tank fractions  and combining
the  analytical  results.    The organic content of the condensate  trap  fraction is
determined  by oxidizing  the NMO to C02  and  quantitatively collecting the effluent
in an  evacuated vessel; then a portion of the C02 is  reduced  to CH/, and  measured by
an FID.  The organic content of the sample tank fraction is measured by  injecting  a
portion of  the  sample into a  gas  chromatographic column to separate the  NMO  from
carbon monoxide  (CO),  C02, and CHA; the NMO are oxidized to C02, reduced  to  CH4,
and  measured by an  FID.    In  this  manner,  the  variable  response   of  the FID
associated with different types of organics is eliminated.
     On October  3,  1980  (45 FR 65956),  EPA  published  Method 25,  "Determination of
Total  Gaseous Nonmethane  Organic Emissions as  Carbon".   Shortly after publication,
testers began to  report  erratic  results  with the method and suggested  a number of
different causes  for  the  imprecision.   As a result,  EPA began  a  program to review
the test method in March 1982.  The EPA completed the review  and proposed revisions
to  Method  25,  designed  to  make   the   njethod  simpler,  more   reliable,  and  more/*—\
precise.   The results of the various studies  on Method 25  are presented  in thef   J
documents listed in Reference Subsection 3-17-H (References  1  through 8).        ^-^
     On February 12, 1988, several  changes were made  to Method 25.  The  studies had
shown  that  the basic  operating principle of Method 25  was sound,  but some changes
in equipment  design and operating  practices would  improve the reliability  of the
method.   These  changes can be discussed!by  dividing the method  into three parts:
Sampling, sample recovery, and analysis.
     The  major  changes  in the sampling equipment  are the addition  of  a  heated
filter, a redesigned  condensate  trap,   and  a different packing  material  for the
condensate trap.  The purpose of the heated filter is to remove organic  particulate
matter from the sample and,  thus,  eliminate  a potential source of imprecision.   It
is heated to a temperature  of 120  °C  (2^8 °F).   The  new trap design is  a simple  U-
tube which  may  be more easily and cheaply produced  than the previous  design.   It
also provides a faster and more  complete sample recovery than  the existing  trap
while  showing equal  collection  efficiency.    The new  packing material  is  quartz
wool, which, compared  to  the  previously  specified stainless  steel packing, is  more
durable and has improved collection efficiency.
     The  major  changes  in the sample   recovery  are a new  oxidation  catalyst,  a
simplified recovery system,  and lower operating temperatures.    The new oxidation
catalyst  has  proven  to  be  very  durable  and  to  provide  100 percent  oxidation
efficiency  for   a  wide  variety  of  organic  compounds at  much  lower  operating
temperatures than the old  catalyst.  Thejredesigned  recovery system has eliminated
some of  the tubing and valving  and,  thus,  reduced  the potential for  sample  loss
during recovery  and  decreased the recovery  time.    The lower   temperatures for
sample recovery will increase  the  life expectancy of the  recovery system materials
and simplify the operation of the system.                                         /*~\
     The major change in the  sample analysis system  is a new separation column for(   J
the nonmethane organics analyzer.   This  new  column provides  separation  of CO,  C02,^>—'
and CH^,  from a  wider range  of organic j compounds   than  the previously  specified
column.

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                                                            Section No.  3.1?
                                                            Date May 31, 1991
                                                            Page 5

      In  addition  to  these major  changes,  there  are  a number of minor  changes,
 particularly in  the areas of quality assurance (QA) and calibration.
      Collaborative testing  of  Method 25 has not been  performed.   However,  results
 for  analysis  of performance audit  samples  have  shown  that the  revised method  can
 meet  the required relative error of +_ 20 percent of the actual concentration of the
 audit gas.
      The  blank  data forms  may  be removed  from  the Handbook  and used  in  the
 pretest, on-site, and posttest operations.  The items/parameters that can cause the
 most  significant errors are designated with an asterisk.

 1.  Procurement of Apparatus and Supplies
      Section 3-17-1  (Procurement of Apparatus and  Supplies)  gives specifications,
 criteria,  and  design  features  for the  required  equipment  and materials.   This
 section can be used  as  a  guide for procurement and initial checks of equipment and
 supplies.  The  activity matrix (Table 1.1) at the  end of  the section is a summary
 of the details given in the text and can be used as a quick reference.

 2.  Pretest Preparations
      Section 3-17-2  (Calibration of Apparatus) describes  the required calibration
 procedures  and   considerations  for  the  Method  25 sampling  equipment.   Required
 accuracies for each  component  are also included.   A pretest  checklist  (Figure 3-1
 in Subsection 3-17-3) or a similar form should be used to summarize the calibration
 and other  pertinent  pretest data.   The  calibration section  may  be  removed along
 with  the  corresponding sections  for the  other  methods and  made  into a separate
 quality assurance  reference manual  for use by  personnel involved in  calibration
 activities.
     Section 3-17-3  (Presampling Operations)  provides  the tester  with  a guide for
 equipment and supplies preparation  for  the  field  test.  A pretest preparation form
 can be used  as  an equipment checkout  and packing list.   Because  of the potential
 for high blank  levels,  special  attention must be  paid in the  preparation of the
 sampling equipment.    Also the  tester  must  ensure  that the  agency  obtains  the
 required audit samples for the test.
     Activity  matrices  for  the  calibration of  equipment  and   the  presampling
 operations (Tables 2.1 and 3-1) summarize the activities.

 3-  On-Site Measurements
     Section3-17-4(On-Site  Measurements) contains  step-by-step procedures  for
 sample collection  and  sample  preparation  for transport.   The  on-site checklist
 (Figure 4.2, Section 3.17.4)  provides  the  tester with a  quick method  of checking
 the  on-site  requirements.   The revised  sampling equipment  and  procedures  were
 designed to help eliminate  the contamination of  the sample  for particulate matter
 from  the source  and  to provide better  collection  of condensible organic compounds
 in the trap and must be closely followed to provide more precise measurements.  The
 audit samples are collected during the field sampling phase.  Table 4.1 provides an
 activity matrix for all on-site activities.

 4.  Posttest Operations
     Section  3-17-5  (Posttest Operations)  presents   the  posttest  equipment
procedures and a step-by-step  analytical procedure for determination of the total
nonmethane gaseous organics  as carbon.   Posttest calibration  is  not required for
 any of the sampling  equipment.  The posttest operations form (Figure 5.1.  Section
 3.17.5)  provides some  key parameters  to be checked by the  tester and laboratory
personnel.   The  step-by-step  analytical  procedure description can be  removed and

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                                                            Section No.  3.1?
                                                            Date May 31,  1991
                                                            Page 6
o
made  into  a  separate  quality  assurance  analytical  reference  manual  for  the
laboratory  personnel.   Initial performance  tests  of both the  condensible  organic
recovery system and the NMO analyzer must be performed before the systems are first
placed into operation,  after  any  shutdown of longer than six months,  or after any
major modification of the  systems.   In  addition  to the  initial  performance  checks,
daily performance checks and calibrations must be performed.   Analysis of two audit
samples is  required.   Strict  adherence to Method  25 analytical  procedures  must be
observed.
     Section 3-17-6 (Calculations) provides the tester with the required equations,
nomenclature, and significant digits.   Because of  the complex nature of the method
and the large  number  of checks, an example data reporting format  is  shown.   It is
suggested  that a  calculator or  computer  be used,  if available,  to  reduce  the
chances of  calculation error.
     Section  3•17-7   (Maintenance)  provides  the  tester  with  a  guide  for  a
maintenance program.   This program is not  required,  but should  reduce equipment
malfunctions.    Activity  matrices  (Tables  5-It  6.1,  and  7-1)  summarize  all
postsampling, calculation,  and maintenance activities.

5.  Auditing Procedures
     Section  3-17-8  (Auditing  Procedure)  provides a description  of  necessary
activities  for conducting  performance and system  audits.   The performance audit of
the sampling and  analytical phase can  be  conducted  using  audit gas  cylinders*—v
supplied  by the  Quality  Assurance Division,  Atmospheric  Research  and  Exposurf    J
Assessment  Laboratory, U.  S.  Environmental Protection Agency.   The data processing-*—/
procedures  and a checklist for  a systems audit are  also  included  in this Section.
Table 8.1 is an activity matrix for conducting the performance and system audits.
     Section 3-17-9 (Recommended  Standards for Establishing  Traceability) provides
the primary standard to which the analytical data should be traceable.

6.  References
     Section  3.17.10  contains  the  promulgated  Method  25  and  Section  3.17.11
contains the references cited throughout the text.
                                                                                  O

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                                                              Section No.  3.17.1
                                                              Date May 31,  1991
                                                              Page 1


1.0  PROCUREMENT  OF APPARATUS  AND  SUPPLIES

      A schematic of the sampling train used  for Method 25 is shown  in Figure  1.1
 and  a  schematic  of  the  analytical  equipment  is  shown  in  Figure  1.2.
 Specifications,  criteria,  and/or design features  are presented in this section to
 aid in the selection of equipment.   Many  of the  sampling train  components can be
 manufacturer  by  the  tester  or other  vendors.     Procedures  and  limits  (where
 applicable)  for acceptance checks are also presented.   Calibration  data  generated
 in the acceptance  checks are to be recorded in the  calibration log book.
      During  the procurement  of  equipment  and supplies,  it is  suggested that  a
 procurement  log  be used to  record  the  descriptive title  of  the equipment,
 identification  number  (if  applicable), and the results of acceptance  checks.
      The  following procedures and descriptions are  only provided as guidance  to  the
 tester and may  not be requirements of the method for the initial ordering  and  check
 out of the  equipment  and  supplies.   The  tester  should note  that  many of  these
 procedures are  required at a  later  step in the sampling and  analytical procedures.
 It is therefore in the best interest of the sampling and analytical firm that  these
 procedures or  other similar  procedures  be instituted  as   routine  practice  for
 checking  new equipment  and supplies to prevent  later  problems  and/or  delays  in
 test programs.   Table  1.1  at  the end of this section contains a summary of quality
 assurance activities for procurement and acceptance of apparatus and  supplies.

 1.1  Sampling

      The  sampling system  consists  of  a heated probe,  heated filter, condensate
 trap,  flow  control  system,  and sample tank (Figure  1.1).    The TGNMO  sampling
 equipment can be constructed  from commercially available components  and components
 fabricated in a machine shop.  Complete sampling systems are  commercially  available
 that have been designed  to  meet all  EPA equipment design  specifications.    The
 following equipment is required:

 1.1.1  Heated Probe - 6.4-mm (1/4-in.) outside diameter (OD)  stainless steel tubing
 with a heating  system  capable of maintaining a gas  temperature at the exit end of
 at least  129°C  (265°F).   The  probe shall be  equipped  with  a thermocouple at  the
 exit end  to monitor the gas temperature,
      A suitable probe  is  shown  in  Figure 1.1.   The nozzle  is  an   elbow fitting
 attached  to  the front end  of  the probe while the  thermocouple is inserted in  the
 side arm  of  a tee  fitting  attached  to the  rear of  the probe.   The probe is wrapped
 with a suitable length  of  high temperature heating  tape,  and  then covered with  two
 layers of glass  cloth insulation and one layer of aluminum foil.
      NOTE:  If it  is not possible to use  a  heating system for safety reasons,  an
 unheated  system with an in-stack filter is a suitable alternative.
      Upon receipt  or after construction,  visually  check  the probe   for  problems,
 and  plug in  the  probe  heating system  to  ensure  it will  heat.    Check  the
 thermocouple  at room temperature to ensure  it is  functional, and check  the  probe
 heating system  in  conjunction with the entire sampling system as described later in
 Subsection 1.1.10.   If desired, it may  be checked separately  by   following  the
 checkout  procedures in Subsection 1.1.10 that relate to the sample probe.

 1.1.2  Filter Holder -  25-mm  (15/l6-in.) inside diameter (ID)  Gelman filter holder
 or equivalent with stainless steel body and stainless steel support screen with  the
 Viton 0-ring replaced by a Teflon 0-ring.  Upon receipt or after construction,

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                                                                  Section No.  3.17.1
                                                                  Date May 31. 1991
                                                                  Page 2
                                                         o
                                           REGULATING
                                             VALVE
                      DUAL RANGE
                       ROTAMETER
           TEMPERATURE
            CONTROLLER
   THERMOCOUPLE:
          I
PURGE VALVE

      THERMOCOUPLE
STACK
WALL
                                           MANOMETER
                        VACUUM PUMP
  ROW
CONTROL
 VALVE
                        STAINLESS STEEL
                        FILTER HOLDER
                 ROTAMETER P"""!-
                     HEATED BOX
              STAINLESS
             STEEL PROBE
                                                                    SAMPLE
                                                                     TANK
                                                                     VALVE
                                                         O
                                                        CONDENSATE
                                                           TRAP
                                                SAMPLE
                                                 TANK
                          Figure 1.1.  Method 25  sampling train.
                                                         O

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                                                         Section No.  3-17.1
                                                         Date May 31, 1991
                                                         Page 3
CALIBRATION STANDARDS
         SAMPLE TANK
                          CARRIER GAS
 SAMPLE
INJECTION
  LOOP
                          SEPARATION
                            COLUMN
           CO,CH4.CO2
INTERMEDIATE COLLECTION
  VESSEL (CONDITIONED
     TRAP SAMPLE)
                                       BACKFLUSH
              NONMETHANE
               ORGANICS
                           OXIDATION
                           CATALYST
                           REDUCTION
                           CATALYST
                            FLAME
                           IONIZATION
                           DETECTOR
              • HYDROGEN
               COMBUSTION
                   AIR
                        DATA RECORDER
        Figure 1.2.  Method 25 analytical equipment.

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                                                              Section No. 3.17.1
                                                              Date May 31,  1991
                                                              Page 4

visually  check  the filter holder for problems, ensure that  the  unit will  properly
hold  a filter and tighten, and, then  check  the filter holder as part of a  unit as
described  in Subsection  1.1.10.   If  desired,  it  may  be  checked separately  by
following  the checkout procedures in Subsection  1.1.10  that relate to  the filter
holder.
     NOTE:  Mention  of   trade  names  or  specific  products does  not  constitute
endorsement by the Environmental Protection Agency.

1.1.3   Filter Heating System - A metal  box consisting of  an inner and  an outer
shell  separated  by insulating material with  a heating element in  the  inner shell
capable of maintaining a  gas  temperature at the filter of 121 ^ 3° C (250 +_ 5°F).
     A suitable  heating  box  is  shown in Figure 1.3.   The  outer shell  is  a metal
box that measures  102 mm  x 280 mm x 292 mm  (4 in. x  11 in. x. 11 1/2 in.), while the
inner  shell is a metal box measuring 76 mm x 229 nun  x 24l mm (3 in. x 9 in. x 9 1/2
in.).  The inner box is supported by 13-mm  (1/2-in.) phenolic rods.  The void space
between the  boxes  is filled with fiberfrax insulation which is  sealed in place by
means  of  a silicon rubber bead around the upper sides of the box.  A removable lid
made  in  a similar manner, with  a  25-mm (1-in.)  gap between the  parts,  is used to
cover  the heating  chamber.
     The  inner box  is  heated with  a 250-watt  cartridge  heater,  shielded  by a
stainless  steel shroud.   The  heater is regulated  by a  thermostatic temperature
controller  set  to  maintain  a  temperature  of  121°C  (250°F)  as  measured  by a
thermocouple  in the gas line  just before the filter.  An additional thermocouple is —-
used to monitor the temperature of the gas behind  the filter.                      f   j
     Upon receipt  or after construction, visually  check the  out-of-stack filter box\_x
for  problems, plug in  the heater to  ensure operation,  check  the  thermocouple at
room temperature to ensure that  it is functional,  and then check the box as part of
the  unit  as described   in  Subsection  1.1.10.    If desired,  it  may  be  checked
separately by following the checkout procedures in Subsection 1.1.10 that relate to
the filter heating system.

1.1.4  Condensate  Trap -  9.5-mm  (3/8-in.) OD 316 stainless steel tubing bent into a
U-shape.   Exact dimensions are  shown in Figure  1.4.   The  tubing  shall be packed
with  coarse   quartz  wool  (8  to  15 um),  to a  density  of approximately  0.11 g/cc
before bending.  While the condensate trap is packed with dry ice in the Dewar, an
ice bridge nay form between the arms  of the condensate trap making it difficult to
remove the  condensate trap.   This problem can  be  prevented by  attaching a steel
plate  between the arms  of the condensate  trap in  the same plane as  the  arms to
completely fill the intervening space.
     Upon  receipt  or after  construction,  visually  check the condensate  trap  for
problems,  ensure  proper  fittings,  ensure  proper  packing,  and  then check   the
condensate trap as part  of a unit as described  in Subsection  1.1.10.   If desired,
it may be checked  separately by following  the checkout procedures  in Subsection
1.1.10 that relate to the condensate trap.

1.1.5   Valve -  Stainless steel  shut-off valve  for starting and  stopping sample
flow.  Upon receipt, visually check the valve for problems and then check the valve
as part of a unit as described in Subsection 1.1.10.

1.1,6   Metering Valve -  Stainless steel control  valve  for regulating  the samplef^
flow rate through  the  sampling train.   Upon receipt, visually  check the valve f
problems and  then check  the  valve as  part of a  unit  as described  in Subsection
1.1.10.

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                                                                   Section  No.  3-17.1
                                                                   Date May 31, 1991
                                                                   Page 5
                                       VACUUM PUMP
                                        CONNECTOR
                SAMPLE
               SHUT-OFF
                VALVE
                         25.4
                         1.0
                       FIBERFAX
                      INSULATION
              DIMENSIONS: -DEI
                          in
lijj/   PROBE
   CONNECTOR
                                             3.175
                                             0.125
                                         CONDENSATE
                                         TRAP PROBE
                                           BULKHEAD
                                          CONNECTOR
                                                                                 J
                PROBE LINE
              THERMOCOUPLE
           TO TEMPERATURE
             CONTROLLER
                           cn
 FILTER HEAT            CONDENSATE
 TEMPERATURE           TRAP PROBE
 CONTROLLER             CONNECTOR
THERMOCOUPLE         THERMOCOUPLE
                             Figure  1.3.   Schematic of out-of-stack filter  box.

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                                                           Section No.  3.17.1
                                                           Date May 31, 1991
                                                           Page 6
                                                                    o
DIMENSIONS:
mm
 in
           0.89
0.375 ^    0.035
   316SS TUBING
                                                                  316SS NUT
WALL
                                                                               O
                                                          COARSE QUARTZ
                                                          WOOL PACKING
                                   2.25
                                                                               O
                        Figure  1.4.   Condensate  trap.

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flFTls.
1
                                                              Section No. 3.17.1
                                                              Date May 31, 1991
                                                              Page 7

1.1.7  Rotameter  - Glass tube with stainless steel fittings,  capable of measuring
sample flow in the range of 60 to 100 cc/min.
     Upon  receipt,  visually  check the  rotameter for problems  and  proper  range,
ensure proper fittings, and  then check  it as part  of the  unit as  described  in
Subsection 1.1.10.  If  desired the unit  may be  checked separately by following the
checkout procedures in Subsection 1.1.10 that relate to the rotameter.

1.1.8  Sample Tank - Stainless steel or  aluminum tank with a minimum  volume  of 4
liters.   Upon receipt  or  after  construction,  visually  check the sample  tank for
problems and  minimum  size,  ensure proper fittings, and  then  check the sample  tank
as  part  of  a unit  as  described  in Subsection  1.1.10.   If desired,  it may  be
checked separately by following  the  checkout procedures in Subsection 1.1.10  that
relate to the sample tank.

1.1.9    Mercury  Nanometer  or  Absolute  Pressure  Gauge  -  Capable  of  measuring
pressure to within 1 mm Hg in the range of 0 to 1,200 mm Hg.   Upon receipt or after
construction,  visually check  the  pressure gauge  for problems,  ensure  proper
fittings, proper  range, and  proper  sensitivity,   and  then check  it  as part  of a
unit as described in  Subsection  1.1.10.   If desired,  it may  be  checked separately
by  following the checkout procedures  in  Subsection 1.1.10  that  relate  to  the
pressure gauge.

1.1.10  Vacuum Pump - Capable of evacuating a container  to an absolute pressure  of
10  mm  Hg.    Upon  receipt,  visually  check  the  vacuum pump for  problems.   Ensure
proper fittings,  attach the pump to a vacuum gauge,  and determine if  the pump  is
capable of evacuating to an absolute pressure of  10 mm Hg.  Check it as  part  of a
unit as described below.  If desired,  it may be  checked separately by following the
checkout procedures below that relate to the pump.
     1.  Calibrate  all   thermocouples  as  described  in  Section  3-17-2.    If  the
         thermocouples are not within 3°C  (5°F) of the true temperature,  reject  or
         repair and recalibrate.
     2.  Calibrate  the  rotameters  as  described in  Section  3.17.2.    If  the
         rotameters cannot  determine  the  flowrate  to  within  10  percent  of  the
         actual flowrate over  the  indicated  range,  reject  or  repair  and  then
         recalibrate.
     3.  Calibrate and  leak check  the  sample tank as  described  in Section 3.17.2.
         The tank is acceptable if no change in tank  vacuum is noted over a 1  hour
         period.
     4.  With  the sample tank evacuated,  assemble the  sampling  train (including
         placing  a filter  in  the filter holder)  as shown in Figure  1.1,  with the
         exception that is not  necessary to use dry ice  to cool  the condensate
         trap.  Plug the probe tip and verify that the tank valve is closed.   Turn
         on the vacuum pump, and evacuate the sampling system  from the probe tip to
         the sample tank valve to an absolute pressure of  10  mm  Hg or less.   Close
         the purge valve,  turn  off the pump, wait a  period of 5  minutes,  and re-
         check the indicated  vacuum.   The  method allows a leak rate of  1  percent
         of the sampling rate,  but for  this initial  check of new equipment it  is
         recommended that the criteria be increased  to  no noticeable  leak.   If a
         leak is  noted,  find  the source of it  and reject, repair,  or replace the
         component(s)  and  repeat  the  leak  check until  satisfactory  results  are
         obtained.
     5.  Release  the  vacuum  and  then  unplug  the  probe tip.    Set the  probe
         temperature  controller  to  129°C  (265°F)   and  the  filter  temperature

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                                                              Section No. 3.17-1
                                                              Date May 31,  1991
                                                              Page 8

         controller  to  121°C  (250°F).   Allow  the probe  and filter  to heat  for
         about 30 minutes.  Close the sample valve, open the purge valve, start the
         vacuum pump,  and set the  flow rate between  60 and  100 cc/min.    If the
         purge system draws  gas  through the probe and filter  at  the desired rate,
         the purge system is acceptable.  If  the  purge system does not provide the
         desired flow rate,  repair  or replace the system or  problem component and
         repeat the check.
     6.  When the temperature  at the exit  ends of the probe  and  filter are within
         the specified  range,  close the purge valve  and stop the pump.   Open the
         sample valve and the sample tank valve.   Using the flow control valve, set
         the  flow  through  the  sample  train  to  the  maximum rate  that would  be
         normally  used  (i.e.,   100  cc/min).   Operate  the  system  for about  30
         minutes, adjusting  the  flow rate as  necessary to  maintain a constant rate
         (+10 percent).   The  temperature  of the  probe  and filter  must remain  in
         the specified  range and the flowrate should  be adjustable.   If  the flow
         rate  and  temperatures  can  be maintained in  the  proper  range,  conduct
         another leak check  as described above in Step 4.   If the flow rate and/or
         temperatures cannot be  maintained  in the proper range,  repair or replace
         system or problem component(s) and repeat sampling check and leak checks.

1.2  Analysis

     The analysis  equipment consists primarily of an organic condensate  recovery
system  for processing  sample  traps  and  a nonmethane  organic (NMO)  analyzer for
analysis of C02 and  NMO.  The  recovery  system can be  constructed from commercially
available components and components fabricated in a machine shop.   The NMO analyzer
can  be  purchased  as  a  commercial  unit  or  assembled  in the  laboratory  by
modification of a packed column gas chromatograph.

1.2.1  Condensate Recovery Apparatus -  The  system for  the  recovery of the organics
captured in  the condensate  trap consists  of a  heat  source, oxidation catalyst,
nondispersive  infrared  (NDIR)   analyzer,  and an  intermediate   collection  vessel
(ICV).  Figure 1.5 is a schematic of a typical system.   The system shall be capable
of proper  oxidation  and recovery, as specified in Section 3.17.5-   The following
major components are required:

     Heat  Source  - Sufficient to heat the  condensate  trap  (including connecting
tubing) to a temperature of  200°C.   A system using both a heat gun and an electric
tube  furnace  is recommended.    Upon  receipt,  visually  check  the heat  gun and/or
electric tube furnace for any  defects.  Check any device for heating before use to
determine if a condensate trap temperature of 200°C can be achieved.

     Heat  Tape  -  Sufficient to  heat the  connecting tubing between  the water trap
and the oxidation catalyst to 100°C.  Upon receipt, visually check the heating tape
for any defects and test to ensure heating of the connecting tubing to 100°C.

     Oxidation  Catalyst - A suitable  length  of  9.5-mm (3/8-in.) OD  Inconel 600
tubing packed with 15 cm (6 in.)  of 3-2-mm (1/8-in.) diameter 19 percent chromia on
alumina pellets.   The  catalyst  material  is packed in the center  of  the catalyst
tube with quartz wool packed on  either  end  to hold it in place.   The catalyst tube    x—-v
shall be mounted vertically  in a 650°C  tube furnace.   After construction, visually   (   j
check the catalyst tube for  problems and test the tube heater to ensure heating to   V	'
650°C.
o

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                                                      Section No.  3.17.1
                                                      Date May 31, 1991
                                                      Page 9
              FLOW METERS
                      \
                                          HEAT TRACE (100°C)
                                   SAMPLE
                                  RECOVERY
                                    VALVE
                  FLOW
                CONTROL
                  VALVE
                                                           SYRINGE PORT
VACUUM PUMP
             Figure 1.5-  Condensate  recovery system.

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                                                              Section No. 3.17.1
                                                              Date May 31,  1991
                                                              Page 10
o
     Water  Trap - Leak  proof,  capable of removing  moisture from the  gas  stream.
Upon  receipt or  after construction,  visually  check the  water trap for  defects,
especially leakage problems.

     Syringe Port - A 6.4-mm (1/4-in.) OD stainless steel tee fitting with a rubber
septum placed in the side arm.  After construction, visually check the syringe port
for defects, especially leakage around the rubber septum.

     NDIR Detector - Capable of indicating C02 concentration in the range of 0 to 5
percent,  to  monitor the progress  of combustion of the  organic  compounds  from the
condensate trap.  Upon receipt, visually check the NDIR detector for defects.  Zero
and span  the analyzer according to the manufacturer's directions.

     Flow-Control Valve - Stainless  steel, to maintain the trap conditioning system
near atmospheric pressure.  Upon receipt, visually check the flow control valve for
defects.

     Intermediate Collection  Vessel (ICV) - Stainless  steel or aluminum,  equipped
with a  female  quick connect.   Tanks with nominal  volumes  of at least 6 liters are
recommended.  Upon receipt, visually check the ICV for defects.
     Determine  the  ICV volume by weighing it while  empty  and then filling it with
deionized  distilled water;  weigh to  the nearest  5 g  and record  the difference
between  the full  and  empty  weights  as the  tank volume  in ml.   Alternatively.
measure the volume of water used to  fill the tank to the nearest 5 ml«
     An alternative to  using  the  rigid containers  is the use of flexible bags
of Tedlar or Teflon film.  However,  the calculations given in Section 3-17-6 are no
longer  appropriate  since the  gas volumes must be  measured directly.   It  is the
responsibility  of  the  tester  to  apply calculations  which  are consistant  with
directly measured gas volumes.

     Mercury Nanometer  or Absolute Pressure  Gauge  - Capable of measuring pressure to
within  1  mm Hg in the range of 0 to 1,200 mm Hg.   Upon receipt,  visually check the
manometer or pressure gauge for defects and proper operating range and precision.

     Syringe -  10-ml gas-tight, glass syringe equipped with an appropriate needle.
Upon receipt, visually check the syringe for defects and proper volume.

1.2.2  NMO  Analyser -  The NMO analyzer  is a gas chromatograph (GC)  with backflush
capability  for  NMO  and  C02  analysis  and is equipped with  an  oxidation catalyst,
reduction catalyst, and  FID.   Figures 1.6 and  1.7  are  schematics  of a typical NMO
analyzer.  This semicontinuous GC/FID analyzer shall be capable of:  (1) separating
CO, C02, and CH4 from NMO; (2) reducing the C02 to CH4, and  quantifying as CH4; and
(3) oxidizing  the  NMO to  C02,  reducing  the C02  to CHa  and quantifying  as CH^,
according to  Section  3-17-5-   The  NMO analyzer  consists of  the  following major
components:

     Oxidation  Catalyst - A  suitable  length  of 9.5-mm (3/8-in.)  OD  Inconel 600
tubing packed with 5-1 cm (2 in.)  of 19 percent chromia on 3-2-mm (1/8-in.) alumina
pellets.  The catalyst material  is packed in the  center of the tube and supported
on either side  by quartz wool.   The catalyst tube  must  be mounted vertically in
650° C furnace.   After  construction, visually  inspect  the  oxidation  catalyst f
defects and ensure that the tube furnace is capable of heating to 650°C.

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                                                     Section  No.  3.17.1
                                                     Date May 31, 1991
                                                     Page 11
                               CARRIER GAS
     CALIBRATION STANDARDS
              SAMPLE TANK—>
                                   i
 SAMPLE
INJECTION
  LOOP
    INTERMEDIATE COLLECTION
<—  VESSEL (CONDITIONED
          TRAP SAMPLE)
                               SEPARATION
                                 COLUMN
                                            BACKFLUSH
                CO, CH4, CO2
              NONMETHANE
               ORGANICS
                                OXIDATION
                                CATALYST
                                REDUCTION
                                CATALYST
           <—HYDROGEN
                                   1
                                  FLAME
                                lONEATION
                                DETECTOR
               COMBUSTION
                   AR
                              DATA RECORDER
Figure 1.6.  Simplified schematic of nonmethane organic (NMO)  analyzer.

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                                                         Section No. 3-17.1
                                                         Date May 31,  1991
                                                         Page 12
                                                           o
                                         COLUMN OVEN
      REDUCTION
       CATALYST
OXIDATION
CATALYST
H2  AIR
                     Figure 1.7.  Nonmethane organic  (NMO) analyzer.
                                                                               O

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                                                              Section No.  3.17-1
                                                             .Pate May 31. 1991
                                                              Page 13

     Reduction  Catalyst  - A 7.6-cm  (3-in.)  length of 6.4-mm  (1/4-in.)  OD Inconel
tubing  fully  packed with 100-mesh pure  nickel  powder.   The catalyst  tube must be
mounted vertically  in a  400°C  furnace.   After construction,  visually inspect the
reduction  catalyst  for  defects and  ensure that  the tube  furnace  is  capable of
heating to 400°C.

     Separation Column(s) - A  30-cm  (1-ft)  length of 3.2-mm (1/8-in.)  OD stainless
steel tubing  packed with 60/80 mesh Unibeads is  followed by a 6l-cm (2-ft) length
of 3.2-mm  (1/8-in.) OD stainless steel  tubing packed with  60/80 mesh Carbosieve G.
The Carbosieve  and  Unibeads columns  must be baked separately at 200°C with carrier
gas flowing through them for 24 hours before initial use.   The columns should then
be  connected  to  each other with  a  1/8-inch  stainless  steel  union.    The column
series  should be  connected to  the sample injection valve  so  that the sample loop
contents will be injected onto  the head of the Unibeads IS  column.

     Sample Injection System  - A 10-port GC sample injection valve fitted with a
sample  loop  properly   sized   to  interface with  the  NMO analyzer   (1-cc  loop
recommended).    Upon  receipt,   visually  inspect  the sample injection  system  for
defects  and  check  for  proper number  of  ports  and valve fitting  size  for  the
connecting tubing used (1/16- or 1/8-in.).

     FID - An FID meeting the following specifications is required:
     1.  Linearity - A linear  response  (+_ 5 percent) over  the operating  range as
        demonstrated by the procedures established in Section 3«17'5-
     2.  Range  - A full  scale  range  of  10  to 50,000 ppm CH4.    Signal attenuators
        shall be  available  to produce a minimum  signal  response of 10  percent of
        full scale.

     Data Recording System -  Analog strip  chart recorder  or  digital integration
system  compatible with  the FID for  permanently recording  the  analytical results.
Upon  receipt, visually  inspect the  data  recording system for  defects  and test
according to manufacturer's instructions.

1.2.3  Other Analysis Apparatus -

     Barometer  -  Mercury,  aneroid,  or  other   barometer capable  of  measuring
atmospheric pressure to within  1 mm Hg.   Upon receipt, visually check the barometer
for defects.

     Thermometer -  Capable  of  measuring the laboratory  temperature  to within 1°C.
Upon receipt,  visually check the thermometer for defects.

     Vacuum Pump  -  Capable of  evacuating to an  absolute pressure  of 10  mm Hg or
less.   Upon receipt,  visually  check  the  vacuum  pump for  defects and test to ensure
capability to reach proper vacuum

     Syringes - 10  ul and 50 ul liquid  injection  syringes.   Upon receipt, visually
check syringes for defects and proper volume.

     Liquid Sample Injection Unit - 316 stainless steel U-tube  constructed as shown
in Figure 1.8 for performing condensible organic  recovery efficiency tests.  After
construction,  visually check the unit for problems,  especially  leakage  around the
rubber septum.

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                                                         Section No. 3.17.1
                                                         Date May 31,  1991
                                                         Page 14
      CONNECTING T
                      INJECTION
                      SEPTUM
     o
                                                  CONNECTING ELBOW
 FROM
CARRIER
DIMENSIONS:
   TO
CATALYST
                                                                              O
                                                           316SS TUBING
                      Figure 1.8.   Liquid sample injection unit.
   O

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                                                                Section  No.  3.17.1
                                                                Date May 31, 1991
                                                                Page 15
   1.3  Reagents and Other Supplies
        Unless otherwise indicated,  all  reagents  should meet  the  specifications of  the
   Committee on Analytical Reagents  of the American Chemical  Society  (ACS);  otherwise,
   use the best available grade.

   1.3.1  Sampling - The following are required for sampling:

        Crushed Dry Ice  - Crushed dry ice is  needed  to  cool the condensate  (U-tube)
   trap during sampling  for  better  collection of  organics and  to keep it  cold  until
   analysis.  There are no specifications on  the  dry ice.

        Coarse Quartz Wool -  Coarse  quartz wool,  8 to  15 urn in size,  is needed to pack
   the condensate  (U-tube) traps  in the laboratory for sampling.  The packing should
   not be conducted in the field prior to  testing  since a trap packed with  new quartz
   wool must  be  taken to  300° C  and then  blank  checked  prior to its use in a  field
   test.  Upon  receipt,  check the specifications  of  the quartz  wool.  If  the proper
   wool has been  sent,  it should be  acceptable.   If  the specifications are  not met,
   reorder the proper item.

        Filters -  Glass fiber filters,  without  organic  binder  are  needed to remove
   organic  particulate  matter  from  the  gas  stream  during  sample  collection.
   Typically,  filters  used for  Method  5  tests  will  be satisfactory,  if no  organic
   binders are present.   If  organic binders  are present,  they may be released during
   testing and positively bias  the  results.    If  the  tester  is  not certain about  the
   presence of  organic binders  in  a glass  fiber filter,  it should  be  placed  in  a
   furnace at 300°C for  2 hours  which will remove any organic binders  present.  This
   procedure,  however, may make  the filter more brittle resulting  in a greater need
   for caution  in handling.    A  check  on the amount of  organic binder  lost can  be
   determined by weighing the filter both before and after heating.   If a significant
   weight loss 'occurs (1 mg per filter),  the  filters probably contain organic  binders.
   They may  still be  used,  but  it  is  recommended that another type of  filter  be
   ordered and checked  in the same  manner, since  removing the  binders with  heat  may
   make the filters too brittle to use safely.

   1.3.2  NMO Analysis  - Several gases are needed for NMO  analysis depending on  the
   exact analyzer used for analysis.  It is critical that all gases  meet  the  require-
   ments for  background  contamination,  to  ensure that  a  low  background  level  is
   present during sample analysis.   The  following gases are needed for NMO analysis:

        Carrier Gases - Depending on the exact  NMO  analyzer,  two  carrier gases will be
   needed for analysis.   Typically  zero  grade  helium  (He)  and zero grade oxygen (0_)
   containing less  than  1 ppm C02  and  less  than 0.1 ppm C as  hydrocarbon  will  be
   required.   Upon receipt, check the label for manufacturer's specifications.  If  the
   gases do  not  meet  the  above  specifications,  they  should  be  returned  to  the
   supplier,  and new gases obtained  and  checked.

        Fuel Gas  - Typically  zero grade hydrogen  (H2) cylinder gas is  needed as a fuel
   gas.   The hydrogen  should be  99-999  percent pure.   Upon  receipt, check the  label
   and manufacturer's specifications.  If the gas does not meet  these specifications,
Itllllreturn it to  the supplier,  and obtain  and check  a new cylinder.

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                                                              Section No. 3-17.1
                                                              Date May 31,  1991      x~
                                                              Page 16                r  A

     Combustion Gas  - Zero grade  air or 02  (as required by  the GC  detector)  is
needed.  Upon receipt, check the specifications.  If the gas does meet the required
specifications, return it to the supplier and obtain new gas and recheck.

1.3.3  Condensate  Recovery  -  Two gases are needed  for  condensate  recovery.   It is
critical  that all gases meet  the requirements  for  background contamination,  to
ensure  that  a low  background  level  is  present  during  sample analysis.    The
following gases are needed for condensate recovery:

     Carrier Gas - Zero  grade air,  containing  less  than 1 ppm C as hydrocarbons is
needed as a carrier for purging the C02 from the trap into the sample tank and then
purging  the  sample from  the  trap during the  oxidation step into  an intermediate
collection  vessel.   Upon  receipt,  the  manufacturer's  specifications should  be
checked  and  the  gases  analyzed  for  background  levels  as  described  in  Section
3.17.5.   If  the  gas  does not meet  the  requirements, it should  be  replaced and the
new gas checked.

     Auxiliary Oxtdant   -  Zero   grade 02 ,  containing   less   than  1 ppm  C  as
hydrocarbons  may  be  needed during  the oxidation  of  the condensate  trap  sample.
Upon receipt,  the  gas  should be checked as  described above.   Zero grade air may be
used instead  of  zero grade 02 if  the  condensible  organic recovery efficiency test
(described in Section 3-17-5) can be passed.

1.3^  Condensate Recovery Performance - The following liquid reagents are needed:

     Hexane  - ACS grade hexane  is needed  for liquid  injection  into  the  liquid
sample injection unit  of the  condensate recovery system to conduct the condensible
organic  recovery efficiency test.   Upon receipt, check the  container of hexane to
ensure that  the ACS  grade specifications are met.  If  they  are not met, return it
to the supplier, obtain a new container, and recheck.
         ••1, ». • ,                                       ;
     Decane  - ACS grade decane  is needed  for liquid  injection  into  the  liquid
sample injection unit  of the  condensate recovery system to conduct the condensible
organic  recovery efficiency test.   Upon receipt, check the  container of decane to
ensure that  the ACS  grade specifications are met.  If  they  are not met, return it
to the supplier, obtain a new container, and recheck.

1.3•5  Calibration Gases for Analysts - The concentrations of all calibration gases
should be traceable  to  National  Institute  for Standards  and Technology  (NIST)
Standards.    For   those  calibration  gases  that  have  corresponding  gaseous  NIST
standards  (i.e.,  propane and carbon dioxide),  traceability should  be established
via the EPA's Revised Traceability Protocol No. 1 (Reference 9).  For the remaining
calibration  gases,   traceability  should  be  established  to gravimetric  NIST
standards.  Traceability to NIST is necessary  because  some  calibration gases with
certificates of analysis have shown significant errors when they were compared with
NIST standards.  Specialty gas  manufacturers should certify  the accuracy of their
calibration gases.
     Revised Traceability Protocol No. 1 compares the concentrations of calibration
gases to  those of  gaseous NIST  Standard Reference  Materials  (SRMs)  or to those of
gaseous  NIST/EPA  Certified Reference  Materials   (CRMs),  which  are  accepted  as   X~N
equivalent to  SRMs (Reference  10).  Although explicit  accuracy specifications for   C   j
these EPA protocol gases  do not exist,  accuracy assessments  by  EPA have found that   ^-—'
many EPA protocol gases are accurate to within 2 percent and that most are accurate

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                                                              Section No. 3.17-1
                                                              Date May 31,  1991
                                                              Page 1?

 to within  5 percent  (Reference  11).   EPA  protocol  gases  may be purchased from most
 specialty  gas manufacturers.
     For  all  calibration gases,  the manufacturer must  recommend a  maximum  shelf
 life  (i.e., the length of time during which the gas  concentration is not expected
 to  change  by  more than  5 percent from its  certified value).   EPA  protocol  gases
 have a  certification period of 18 months, after which they should be recertified.
 Specialty  gas manufacturers should be able to produce stability data to support  the
 maximum  shelf  life  recommendation.    The data  should  be  for the  same compound,
 balance gas, and approximate concentration as requested.
     Do  not  store  the  calibration  gas  cylinders  in  areas  subject  to  extreme
 temperature   changes.    Before  each  calibration,   check  the  pressure  of  the
 calibration gas in the cylinder and replace any cylinders with a pressure less than
 1500 kilopascals (or  200 Ib/sq. in.).
     The following calibration gases are required.

     Oxidation  Catalyst Efficiency Check Calibration Gas - A calibration gas with a
 nominal  concentration of 1  percent  methane in  air  is  required  for the oxidation
 catalyst  efficiency  check.    Upon  receipt  of  the  calibration  gas,  check  its
 certificate of  analysis  to  ensure that  the  correct concentration  has  been  sent.
 Verify  its certified concentration against calibration  gases  currently being used
 for  analysis.   Be certain  that balance  gas  differences do not  cause measurement
 errors  in  the analyzer used  for  verification.   The  verified  concentration should
 agree within  2  percent of the certified  concentration.   If 2 percent agreement is
 obtained,  the certified  concentration can be used.   If  the agreement is between 2
 and 5 percent,  the verified concentration can be used.  If  the agreement is greater
 than  5  percent,   first  inspect  the  analyzer   for  malfunction  and  reverify  the
 calibration gas.   If the  reverified agreement  is   also  greater than  5 percent,
 consult  with  the specialty  gas manufacturer about replacement of the  calibration
 gas.
     The  organic condensate  recovery system  oxidation  catalyst  efficiency  check
 compares  the  concentrations  of  the  methane  and  C02   calibration  gases.    The
 concentrations  of the  two  calibration gases  must   agree  within  2 percent.   Be
 certain to compare the calibration gases  on a ppm carbon basis.  If such agreement
 is not  obtained,  the problem may lie  in  the  catalyst or in the calibration gases.
 Inspect or replace the  catalyst and  reverify the calibration gases' concentrations
 before  repeating the  check.    Consult with  the specialty  gas manufacturer  about
 replacement of  the calibration gases if the lack of agreement persists.

     7/WO Response  Linearity and  Calibration  Gases - Three calibration gases with
 nominal concentrations of 20, 200,  and. 3»000 ppm  propane  in  air are required for
 the NMO linearity check  and to determine  the  calibration  response  factor.   Upon
 receipt of the  calibration gases, check  their certificates of analysis to ensure
 that  the   correct   concentrations  have  been  sent.     Verify   the   certified
 concentrations  against  SRMs using revised  Traceability  Protocol No.  1  or against
 calibration gases currently being used for analysis as described in Section 3-17-5-
Be certain that balance  gas differences do not  cause  measurement errors in  the
 analyzer used for certification.   The  verified  concentration should agree within 2
percent of  the  certified concentration.  If 2 percent agreement  is obtained,  the
 certified concentration can  be  used.   If the agreement  is  greater than 5 percent,
 first inspect the  analyzer for malfunction  and reverify the  calibration  gas.   If
 the reverified agreement is also greater than 5 percent,  consult with the specialty
gas manufacturer about replacement of the calibration gas.

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                                                             Section No.  3.1?
                                                             Date May 31, 1991
                                                             Page 18
•'O
     C02 Response  Linearity  and Calibration Gases - Three  calibration gases with
nominal concentrations of 50 ppm, 500 ppm, and 1 percent carbon dioxide in air are
required to determine  the  overall  mean C02 response factor.   Upon receipt of the
calibration gases, check their certificates of analysis to ensure that the correct
concentrations have been  sent.   Verify  the  certified  concentrations against SRMs
using revised Traceability  Protocol  No.  1 or  against  calibration gases currently
being used for  analysis  as described in Section 3-1?-5-   Be certain that balance
gas  differences  do  not  cause  measurement  errors  in  the  analyzer used  for
certification.   For  example, carbon dioxide  in air response  factors  will differ
from  carbon  dioxide  in  nitrogen  response  factors  for  nondispersive  infrared
analyzers due to pressure broadening effects.   The  verified concentration should
agree within 2 percent of  the  certified  concentration.   If 2 percent agreement is
obtained, the certified concentration can  be used.   If the agreement is between 2
and 5 percent, the verified concentration can be used.   If the  agreement is greater
than  5  percent,  first  inspect the  analyzer  for malfunction  and  reverify  the
calibration gas.   If  the reverified  agreement is  also  greater  than  5 percent,
consult with  the specialty gas  manufacturer about replacement of the  calibration
gas.
     The analyzer linearity check and NMO calibration requires  10  percent agreement
between the propane and C02  calibration gases.  Be sure to  compare  the  calibration
gases on a ppm  carbon basis.  If such   agreement  cannot  be obtained, inspect the
analyzer for  malfunction and  reverify the  calibration  gases.   Consult  with the^^
specialty gas manufacturer  about replacement of the calibration gases if the lacfA
of agreement persists.                                                           V_>X

     NMO Analyser System Performance Check Calibration Gases - The  four following
calibration gases are needed for the NMO  analyzer system check:
     1. Propane  Mixture -  A  calibration  gas with nominal concentrations of 50 ppm
        carbon  monoxide,  50 ppm methane,  2 percent  carbon dioxide,  and  20 ppm
        propane  in air is  required  for the NMO analyzer system performance  check.
        Upon receipt of  the  calibration  gas, check its certificate  of  analysis to
        ensure  that   the  correct  concentrations  have been sent.    Replace the
        calibration gas if  the  purchase  specifications have not been met.   If the
        specifications have  been met,  conduct  the NMO  calibration  check.   The
        response factor for  this calibration gas should be  within  5  percent of the
        overall  mean response factor for the propane in air calibration gases.  If
        such agreement cannot  be obtained,  inspect  the equipment  for  malfunction
        and verify  the concentrations of  the components in the calibration gas.
        Consult   with  the  specialty  gas  manufacturer about  replacement  of the
        calibration gas if the lack of  agreement persists.
     2. Hexane Calibration Gas - A. calibration  gas with a nominal  concentration of
        50 ppm  hexane  in air is required  for  the NMO analyzer system  performance
        check.   Upon  receipt of the  calibration gas,  inspect its  certificate of
        analysis to ensure  that  the  correct concentration has been  sent.  Replace
        the calibration gas  if  the  purchase specifications  have not been met.  If
        the specifications have  been met,  conduct the NMO calibration  check.  The
        response factor for  this calibration gas should be  within  5  percent of the
        overall  mean response factor for the propane in air  calibration gases.  Be,...
        sure to  compare  the calibration gases  on a  ppm  carbon basis.   If suq  A
        agreement cannot  be obtained, inspect the equipment  for malfunction and, i\	J
        possible, verify the concentration of the  calibration gas with  an  analyzer
        employing  a  different  analytical  principle   (e.g.,  gas  chromatography).
        Consult   with   the  specialty  gas  manufacturer about  replacement  of the

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                                                      Section No.  3.17.1
                                                      Date May 31, 1991
calibration gas if the lack of agreement persists.
Toluene Calibration Gas - A calibration gas with a nominal concentration of
20 ppm  toluene in air is required for the NMO  analyzer system performance
check.   Upon  receipt of  the calibration  gas,  check  its  certificate  of
analysis to ensure  that  the correct concentration has  been  sent.   Replace
the calibration gas  if the purchase specifications have not been  met.   If
the specifications have  been met,  conduct the NMO calibration check.   The
response factor for this calibration gas  should be within  5  percent of the
overall mean response  factor for the propane  in air  calibration gases.   Be
sure  to compare  the  calibration gases  on a ppm carbon  basis.    If  such
agreement cannot be obtained, inspect the equipment for malfunction and,  if
possible, verify  the concentration of the calibration gas  with an analyzer
employing  a different analytical  principle (e.g.,  gas  chromatography) .
Consult  with  the specialty  gas  manufacturer  about  replacement  of  the
calibration gas if the lack of agreement persists.
Methanol Calibration Gas - A calibration gas with a nominal concentration
of  100  ppm  methanol  in  air is  required  for  the NMO  analyzer  system
performance  check.    Upon  receipt  of  the  calibration  gas,  check  its
certificate of analysis  to ensure  that  the correct  concentration  has  been
sent.   Replace the calibration gas if the purchase specifications  have not
been met.  If the specifications have been met,  conduct the NMO calibration
check.   The response  factor  for this calibration gas  should be  within 5
percent  of  the   overall  mean  response  factor  for the  propane  in  air
calibration gases.   Be  sure to  compare  the  calibration gases  on a  ppm
carbon basis.  If such agreement cannot be obtained ,  inspect the equipment
for  malfunction  and,  if  possible,  verify  the   concentration  of  the
calibration with  an  analyzer  employing  a different analytical  principle
(e;g., gas chromatography).   Consult the  specialty  gas manufacturer about
replacement of the calibration gas if the lack of agreement persists.
Note;  Little  is  currently known about  the stability of calibration gases
containing methanol  in  air..   Special  attention  should  be given  to  the
stability of this calibration gas.

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                                                              Section No. 3.17.1
                                                              Date May 31,  1991
                                                              Page 20

       Table 1.1.    ACTIVITY MATRIX FOR PROCUREMENT OF APPARATUS AND  SUPPLIES
                                                               o
Apparatus
Sampling

Heated probe
Filter holder
Filter heating
system
Condensate trap
Valve
Metering valve
 Acceptance limits
Frequency and method
   of measurement
Action if
requirements
are not met
Stainless steel cap-
able of heating to
129°C (365°F) at
exit end
Upon receipt, check
heater and thermo-
meter with system
Repair or
replace, and
recheck
Stainless steel with
inside diameter of
25 mm (15/16 in.)
and Teflon 0-ring
Check unit to ensure
that filter is held
properly
Repair or
replace, and
recheck
Metal box consisting
of an inner and an
outer shell separ-
ated by fiber fran
insulation with a
heater capable of
maintaining a gas
temperature of 121°C
+3°C (250 +5°F)
Visually check, ensure
heater is operational,
check thermocouple at
room temperature,
check box as part of
the unit (Subsection
1.1.10)
Repair or
replace and
recheck
                                                                                   O
9.5 mm (3/8 in.)
OD 316 stainless
steel tubing U-tube
shaped, packed with
coarse quartz wool
Visually check, ensure
proper fittings,
proper packing, check
as part of unit
Repair or
replace and
recheck
Stainless steel
shut-off valve
Visually check valve,
check as part of unit
Repair or
replace and
recheck
Stainless steel
control valve
Visually check valve,
check as part of unit
Repair or
replace and
recheck
Rotameter
(Continued)
Glass tube with
stainless steel
fittings, capable
of measuring sample
flow of 60 to 100
cc/min
Visually check, ensure
proper range and
proper fittings, check
as part of unit
Reject or
repair, then
recalibrate
                                                                                   O

-------
                                                              Section No.  3.1?.l
                                                              Date May 31.  1991
                                                              Page 21
Table 1.1   (Continued)
Apparatus
 Acceptance limits
Frequency and method
   of measurement
Action if
requirements
are not met
Sample tank
Stainless steel or
aluminum tank with
a minimum volume of
4 liters
Visually check, ensure
proper fittings, min-
imum size, check as
part of unit
Repair or
replace and
recheck
Mercury manometer
or absolute
pressure gauge
Capable of measur-
ing pressure  to
within 1 mm Hg. in
;the range of  0 to
1,200 mm Hg
Visually check, ensure
proper fittings,
range, sensitivity,
check as part of unit
Determine
correction
factor or
reject
Vacuum pump
Capable of evacu-
ating  to an absolute
pressure of 10 mm
Hg
Visually check, ensure
proper fittings, de-
termine for evacuating
10 mm Hg, check as
part of unit
Repair or
replace and
recheck
Analysis

Condensate
recovery apparatus

 1. Heat source
 2. Heat tape
 3.  Oxidation
    catalyst
 4.  Water trap
 5-  Syringe port
(Continued)
Sufficient to heat
condensate trap to
200° C

Sufficient to heat
connecting tubing
to 100°C

9.5 mm (3/8 in.) OD
Inconel 600 tubing
packed with 15 cm
(6 in.) of 3-2 cm
(1/8 in.) diameter
19 percent chromia
or alumina pellets

Leak proof, capable
of removing moisture
from gas stream

6.4 mm (1/4 in.) OD
stainless steel
Visually check, con-
duct heat check
Visually check, con-
duct heat check
Visually check
Repair or
replace and
recheck

Replace and
recheck
Repair or
replace and
recheck
Visually check, con-
duct leak check
Visually check
Repair or
replace and
recheck

Repair or
replace and
recheck

-------
Table 1.1  (Continued)
                                                              Section No.  3-17.1
                                                              Date May 31, 1991
                                                              Page 22
                                                                    o
Apparatus
 6. NDIR detector
 7. Flow-control
    valve
 8.  Intermediate
    collection
    vessel

 9.  Mercury mano-
    meter or
    absolute pres-
    sure gauge
 10. Syringe
NMO Analyzer

 1. Oxidation
    catalyst
 2. Reduction
    catalyst
 Acceptance limits
Capable of indicat-
ing C02 concentra-
tion in the range of
0 to 5 percent

Stainless steel
Stainless steel or
aluminum, nominal
volume of 6 liters

Capable of measur-
ing pressure to
within 1 mm Hg in
the range of 0 to
1,200 mm Hg

10 ml gas-tight,
glass
Suitable length of
9-5 ran OD Inconel
600 tubing packed
with 5.1 cm of 19
percent chromia on
3.2 mm alumina
pellets

7.6 cm length of 6.4
mm OD Inconel tubing
packed with 100 mesh
pure nickel powder
Frequency and method
   of measurement
Visually check, check
pressure rating
Visually check, ensure
proper volume
Visually check, ensure
ensure proper sensi-
tivity
Visually check
Visually check
Visually check
Action if
requirements
are not met
                        Repair or
                        replace and
                        recheck
Repair or
replace and
recheck

Repair or
replace and
recheck

Determine
correction
factor or
reject
Repair or
replace and
recheck
O
Replace and
recheck
Replace and
recheck
(Continued)
                                                                                        O

-------
                                                              Section No.  3.17-1
                                                              Date May 31,  1991
                                                              Page 23
Table 1.1  (Continued)
Apparatus
Separation
column
Sample injec-
tion system
 5. FID
 6. Data recording
    system
 Acceptance limits
30 cm length of 3-2T
mm OD stainless
steel tubing packed
with 60/80 mesh
Unibeads IS followed
by 6l cm length of
3.2 mm OD stainless
steel tubing packed
with 60/80 mesh
Carbosieve G

10-port GC sample
injection valve
fitted with a
sample loop

A linear response
of +_ 5 percent over
operating range of
10 to 50,000 ppm
CHA, minimum signal
response of 10 per-
cent of full scale

Analog strip chart
compatible with FID
Frequency and method
   of measurement
                                          Visually check
Visually check, sample
loop should be of
proper size to inter-
face with NMO analyzer

Upon receipt use
procedure established
in Section 3-17.5
Upon receipt check as
recommended by manu-
facturer
                                                              Action if
                                                              requirements
                                                              are not met
                        Replace and
                        recheck
                                                                  Repair or
                                                                  replace and
                                                                  recheck
                                                              Return to
                                                              manufacturer
                                                              or repair
                                                              and recheck
                                                              Repair or
                                                              return to
                                                              manufacturer
Reagents and
other supplies
Sampling

 1. Crushed dry
    ice

 2. Coarse quartz
    wool
 3. Filters
(Continued)
No specifications
8 to 15 urn in size
Glass fiber filters
without organic
binders
None
Upon receipt check
manufacturer's speci-
fications

Check for presence of
organic binders
                                                              None
                                                              Return to
                                                              manufacturer
                                                              Return to
                                                              manufacturer
                                              '    J  "7
                                              ,'  -v '\
                                              /  < A) .

-------
Table 1.1  (Continued)
                                                              Section No. 3-17-1
                                                              Date May 31, 1991
                                                              Page 24
                                                               o
Apparatus
 Acceptance limits
Frequency and method
   of measurement
Action if
requirements
are not met
NMO analysis

 1. Carrier gas
 2. Fuel gas
 3- Combustion gas
As specified by
owner's manual, less
than 1 ppm C02 and
0.1 ppm C as hydro-
carbon

As specified by
owner's manual
As specified by
owner's manual
Upon receipt check
label and manufactur-
er's specifications
Upon receipt check
label and manufac-
turer's specifications

Upon receipt check
label and manufactur-
er's specifications
Return to    .
supplier and
check new gas
Return to
supplier and
check new gas

Return to
supplier and
check new gas
                                                                                    O
Condensate
analysis

 1.  Carrier gas
 2. Auxiliary 0.,
 3.  Hexane
  .  Decane
Zero grade air con-
taining less than
1 ppm C as hydro-
carbon

Zero grade 02 con-
taining less than
1 ppm C as hydro-
carbon

ACS grade hexane
ACS grade decane
Same as above
Same as above
Visually check to
ensure ACS grade
Same as above
Same as above
Same as above
Return to manu-
facturer and
check new reagent

Same as above
(Continued)
                                                                                    O

-------
Table 1.1  (Continued)
                                                              Section No. 3-17.1
                                                              Date May 31, 1991
                                                              Page 25
Apparatus
 Acceptance limits
Frequency and method
   of measurement
Action if
requirements
are not met
Calibration gases
for analysis

 1. Oxidation
    catalyst
    efficiency
    check calibra-
    tion gas

 2. FID linearity
    and NMO cali-
    bration gases
 3. C02 calibra-
    tion gases
Gas mixture with
nominal concentra-
tion of 1 percent
methane
Three gas mixture
standards with
nominal propane
concentrations of
20, 200 and 3000 ppm

Three gas mixture
standards with
nominal C02 concen-
trations of 50, 500,
and 1 percent in air
Visually check
specifications
Check specifications,
compare against
NBS-SRM propane or
previous calibration
gas

Check specifications,
compare against
previous calibration
gases or NBS-SRM
No. 2622 (2% C02 in
N2) diluted with 20%
zero oxygen
Return to
supplier, order
from new
supplier
Return to
manufacturer
Return to
manufacturer
NMO analyzer
system check
calibration gas

 1. Propane
    mixture
 2. Hexane gas
    standard
 3-  Toluene gas
    standard
 4.  Methanol gas
    standard
Gas mixture contain-
ing (nominal) 50 ppm
CO, 50 ppm CHA, 2%
C02, and 20 ppm C3H8
in air

Gas mixture contain-
ing (nominal) 50 ppm
hexane in air

Gas mixture contain-
ing (nominal)
20 ppm toluene

Gas mixture contain-
ing (nominal) 100
ppm mehanol in air
Check specifications,
conduct calibration
check which should be
within 52 of initial
NMO response factor

As shown above
As shown above
As shown above
Return to
manufacturer,
check new gas
As shown above
As shown above
As shown above

-------
o
o
o

-------
                                                        Section No. 3.17.2
                                                        Date May 31, 1991
                                                        Page  1
 2.0   CALIBRATION OF  APPARATUS

       Calibration  of  the  apparatus  is one  of the  most important  functions  in
maintaining data  quality.   The  detailed calibration procedures  included  in this
section were  designed  for  the sampling equipment  specified in Method  25  and de-
scribed in  the  previous section.  The  calibration of  the analytical equipment is
described  in  the  section  detailing  the  analytical  procedures,  Section  3«17-5.
Table 2.1 at the end of this section  summarizes  the quality assurance functions for
the calibrations addressed in this section.  All calibrations including  the analyt-
ical equipment should be recorded on  standardized forms and retained in  a calibrat-
ion log book.

2.1  Sample Metering and Volume Systems

2.1.1   Sample Tank  Volume  -  The volume of  the  gas  sampling tanks used  to for
sampling and as intermediate collection  vessels  must be determined  as follows:
     1.  Mark or number each tank so  that it is  uniquely identified.
     2.  Weigh each tank empty to the nearest  5  g-
     3.  Fill the tank with distilled or deionized water  and reweigh to nearest 5
         g-
     4.  Record the  data on Figure 2.1 or similar form  and  calculate  the  sample
         tank volume.
     5.  Alternatively,   the volume of  the water used to  fill  each tank  may be
         determined to the  nearest 5 nil.  It is extremely  important that all the
         water is removed from the tank  after  calibration.

2.1.2  Volume of Sampling Train from  Probe  Tip to Sample Tank Valve - The volume of
the sampling train from  the probe tip to the sample  tank valve must be determined
as follows:                                     '
     1.  Assemble the sampling train  in the same manner  as  it will be  used  in the
         field.
     2.  Leak check the sampling  system  as  described below in Section 2.1.3-
     3.  After the train passes the leak check,  attach a sample tank that has been
         calibrated and is full of air at ambient pressure to the  sampling system.
     4.  With the  inlet  still plugged  from  the leak check, open the  sample tank
         valve,  flow control  valve,  sample valve,  and purge valve to  ensure that
         the tank is at  ambient  pressure.   Note that the mercury  U-tube manometer
         is reading zero.
     5.  Shut  the sample tank valve and start the purge pump (or other  pump  of the
         tester's  choice).
     6.  After approximately  2 min,   shut  the purge valve  and then  turn  off the
         purge pump.
     7.  Open  the  sample tank  valve and  read and record the vacuum.
     8.  Record  these data  and the barometric  pressure  on Figure 2.2  or similar
         form  and  then  calculate  the volume of the sampling train.
     9.  Repeat  steps 4  through 8 twice.  The calculated sampling  train  volume used
         for the  leak  checks  during testing  will be  the  average  of the  three
         calculated volumes.   If the equipment is  similar or the components are
         interchangeable  for all  the  Method  25  sampling  systems  used,  the volume
        from  the  probe  tip to the sample  tank  valve only needs  to  be  determined
         for one system.

-------
                                                        Section No.  3-17-2
                                                        Date May  31,  1991
                                                        Page   2
o
Sample
Tank No.






Date
Calibra-
ted






Initial
Weight/Volume ,
g/ml*






Final
Weight/Volume ,
g/ml*
...





Sample Tank
Volume ,
ml*






Calibrated
By,
initials

••'••:


• •

*Weight measured to the nearest 5 £ or volume measured to the nearest 5 ol.


Figure 2.1.  Sample tank and intermediate collection vessel volume determination.
                                                                                    O
                                                                                    o

-------
                                                         Section No. 3.17.2
                                                         Date May 31,  1991
                                                         Page  3
 Calibrated By
           Date Calibrated
System Assembled

Tank No.
           System Leak Checked

           Tank Volume, ml  	
Barometric Press., mm Hg
Are sampling train components similar and/or interchangeable? 	
Will the calculated sampling train volume be used for all trains?
Run
No.
1
2
3
Vacuum
Reading, mm Hg



Calculated
Volume , ml



Remarks



Average calculated volume
     of sampling system
               ml
     Calculated volume, ml  =
     Calculated volume, ml   -
    Vacuum reading, mm Hg X Tank volume, ml
 Barometric press,  mm Hg - Vacuum reading, mm Hg

     (	) X (	 )   =      	 ml
     Average volume, nil
=  Run 1 + Run 2 + Run 3  =
            3
ml
Figure 2.2.  Determination of sample train volume from probe tip to sample valve.

-------
                                                         Section No.  3.17.2
                                                         Date May 31,  1991
                                                         Page  4


2.1.3   Rotametevs  -  Two  rotameters  are needed,  one for  purging the  sampling
system and  a second for  controlling  the rate of  sample collection.  Since  the
sampling  rotameter is  used  to  determine  flow  rate  and   maintain  a  constant
sampling rate, it  must  have an accuracy of +_ 10%  for the flow  rate  used (60 to
100 cc/min) and a  precision of  +_  5% over its  range.   The rotameter used  to purge
the sampling train  serves  only  as an  indicator of  the flow  rate and its  readings
are not used in  any emission calculations;  therefore, the accuracy of +_ 10%  and
precision of +_ 5# do not apply after its initial calibration.

     Initial Calibration  - Both rotameters should be calibrated as  part of  the
sampling system when first purchased'  and at any time  the posttest check  yields a
calculated sample volume that is not  within 10% of the actual sample volume (for
sampling rotameter  only)  or erratic  behavior  is noted (for  both rotameters).   A
calibrated wet test meter,  calibrated dry gas meter, or  a properly  sized bubble
meter should be used to calibrate the rotameters.
     Before its initial use in  the field, each rotameter should be calibrated as
part of the entire sampling system as described below.
     1. Leak check the rotameter as part of the sampling system as follows:
        a. Temporarily attach a suitable rotameter (e.g., 0-40 cm3/min)  to the
           outlet of the purge system.
        b. Plug the inlet to the probe.  Shut  the sample tank valve and open the
           flow control valve, purge valve,  and the sample valve.  Evacuate the
           entire sampling system to 10 mm Hg.
        c. Note the flow rate as indicated by  the rotameter.
        d. A leak of £0.02 L/min must be obtained;  leaks >0.02 L/min must be
           eliminated.
        e. Close the purge valve and turn off  the pump.
        f. Note the vacuum reading.
        g. Wait five minutes and take another  vacuum reading.
        h. If the pressure has changed by more than 20 mm Hg, the leak should be
           found and corrected.
     2. Attach a wet test meter, bubble meter, or calibrated dry gas meter to
        the inlet of the probe.
     3- Run the pump  for 15 minutes  with the flow rate set  in  the  midrange  (80
        cc/min) to  allow  the pump to warm up and  to permit the interior surface
        of the wet test meter to become wet.
     4. Collect  the information  required  in  the  forms  provided [Figure  2.3A
        (English  units)  or  Figure  2.3B (metric  units)]  using  sample  volumes
        equivalent  to at least  five revolutions of the test  meter or 10  minutes,
        whichever  is greater.   Three independent runs must  be  made  covering the
        top, middle,  and bottom of  the flow  rate range (i.e., 60,  80,  and  100
        cc/min).
     5. Calculate  the Yj  for  each run as shown on the data  forms.   The  Y should
        be  in  the  range  of 0.9  to  1.1 and  the  values of  Yt  should be in  the
        interval Y  +_ 0.05Y,  where Y is the average for  three runs.   If  not,  re-
        calibrate,  repair, or replace the rotameter.   Otherwise, the Y (calibra-
        tion factor)  is  acceptable  and  is  to  be  used for future checks  and
        subsequent  test runs.   Alternatively,  if the  Yt's are acceptable and the
        Y is outside  the range of 0.9 to  1.1,  the rotameter may be  remarked to
        reflect  the corrected  readings.   The  corrected readings will  then be
        used for  testing  and  future calibrations.   The  completed form should be
        forwarded to the supervisor for approval,  and then  filed in the   calibra-
        tion log book.
o
o
o

-------
Date
                  Calibrated by
Meter system no.
Primary meter no.
Barometric pressure, Pn = 	 in. Hg   Ambient temperature 	
                                    	, dry gas 	, or bubble meter
Type of primary meter:  wet test
Primary meter readings
Initial
reading
(vpl),a
ft3



Final
reading
(vpf),a
ft3



Initial
temp,°F
(tpl)
op



Final
temp,°F
(tpf)
op



Press
drop
(Vc
in.
W



Rotameter readings
Initial
reading
(vs,).b
ft3 or
ft3 /min



Final
reading
(vs,)b
ft3 or
ft3 /min



Initial
temp

op



Final
temp
(tsf)
op



Press
drop
(Ds),c
in.
H20



Time
min
(e),d
min



Calibration
factors
(YJ,"



(Y)



0  Volume passing through the meter using the initial and final readings;  requires a minimum of at
   least five revolutions of the meter.
b  Volume passing through the meter using the initial and final readings or  the  indicated flow rate
   using the initial and final flow rate setting.
c  Pressure drop through the meter used to calculate the meter pressure.
d  The time it takes to complete the calibration run.
e  With Y defined as the average ratio of volumes for the primary meter compared to the flowmeter
   calibrated, Y must be 0.9 to 1.1 and Y1 = Y + 0.05Y thus:
   *i '
                                        F] [P. *  (D/13.6)]
               Vtl)/2je[(tpl + tpf)/2 + 460°F][Pm
                -(Eq. 2-3),Y =
                                                                            Y  +  Y  •*• Y
                                                                            xl    *2    I3
                                                                                                -(Eq.2-4)
                 Figure 2.3A.   Rotameter calibration data form (English units).
                                                                                                            T3 O CO
                                                                                                            {0 P (D
                                                                                                            oq ct o
                                                                                                            CD (D rt
                                                                                                                M-
                                                                                                              3 O
                                                                                                            U1 P 3

                                                                                                              OO O
                                                                                                                LO
                                                                                                              VD
                                                                                                                to

-------
Date
             Calibrated by
Barometric pressure, Pra = 	
Type of primary meter: wet test
Meter system no.
                                    mm Hg  Ambient temperature
Primary meter no.
        °C
                                     ,  dry gas
                     ,  or bubble meter
Primary meter readings
Initial
reading
(vpl),a
m3



Final
reading
b
m* or
m3 /min



Final
reading
(V)b
m3 or
m3 /min



Initial
temp

°C



Final
temp
(tsf)
°C



Press
drop
(Ds).c
mm
H20



Time
min
(9)/
min



Calibration
factors
(YJ."



(Y)



0  Volume passing through the meter using the initial and final readings and requires a minimum of at
   least five revolutions of the meter.
b  Volume passing through the meter using the initial and final readings or the indicated flow rate
   using the initial and final flow rate setting.
0  Pressure drop through the meter used to calculate the meter pressure.
d  The time it takes to complete the calibration run.
e  With Y defined as the average ratio of volumes for the primary meter compared to the rotaineter
   calibrated, Y must be 0.9 to 1.1 and Yj = Y +_ 0.05Y thus,
(Vpf  -'VpilKt.i  * fcsf)/2 + 273°K][Pn  * (Dp/l3.6)]

    r  + Vsl)/2]9[(tpl  * tpf)/2 + 273°K][PB  + (E
             (Eq. 2-7), Y =
                                                                                              (Eq. 2-8)
                 Figure 2.3B.  Rotameter calibration data form (metric units).
                                                                                                      13 o en
                                                                                                      P f» CO
                                                                                                      m ct o
                                                                                                      (D CO ff
                                                                                                          H-
                                                                                                        s: o
                                                                                                        o o
                                                                                                          2:
                                                                                                        cu o
                                                                                                               LO
 O
                                               o
                                                            o

-------
                                                         Section No. 3.17.2
                                                         Date May 31.  1991
                                                         Page  7
     Posttest  Calibration Check -  After each  field  test series,  calculate  the
volume  of  sample  that  should have  been collected  during the  sample run  and
compare  the results  with the actual volume collected.   If  the calculated volume
and  the  actual volume collected are within 10% of each  other  on  the average for
the  three  runs, no recalibration is  needed.   If the average  sample volumes  are
not  within 10%, the  sampling rotameter should be recalibrated.   When either the
sampling rotameter or purge rotameter exhibits erratic  behavior  during sampling
or purging of  the  system, it should be recalibrated.  Performance  of a posttest
calibration does not necessitate changes in the emission calculations.

2.3  Thermocouples

     The thermocouples on the  sample  probes  and the  filter  heating system should
be initially compared with a mercury-in-glass thermometer that meets ASTM E-l No.
63C or 63F specifications:
     1.  Place  the thermocouples to be calibrated and the mercury-in-glass
         thermometer in a bath of boiling water.  Compare the readings after
         the bath temperature  stabilizes  and  then record them  on  the calibration
         data form, Figure 2.4 or equivalent.
     2.  Allow  both  the  thermocouple  and reference thermometer to  come  to room
         temperature.    Compare  the  readings  after  the  temperature  readouts
         stabilize.
     3.  The thermocouple is acceptable if the values agree within 3°C (5.4°F) at
         both points.
     4.  Prior  to each   field trip,  compare  the   temperature  reading of  the
         mercury-in-glass thermometer  at  room  temperature  with   that of  the
         thermocouple that is part of the metering system.  If the values are not
         within 3°C  (5.4°F)  of  each  other,  replace  or  recalibrate  the
         thermocouple.
     5.  No  posttest calibration of  the thermocouples  is  required  unless they
         demonstrated erratic behavior during the sampling.

2.*f  Barometer

     The field  barometer should be adjusted initially and before each test series
to agree within 2.5*1 mm  (-0.1 in.)  Hg with a mercury-in-glass barometer'or with
the  pressure value  reported from a nearby  National Weather Service Station and
corrected  for  elevation.   The  tester should  be aware that  the National Weather
Service readings are normally corrected to sea level; uncorrected readings should
be obtained.    The correction  for  the elevation  difference between  the weather
station and the sampling  point should be  applied  at  a rate  of  -2.5 mm Hg/30 m (-
0.1 in. Hg/100  ft) elevation increase, or vice versa for elevation decrease.

2.5  Absolute Pressure Gauge

     The absolute pressure gauge should  be  calibrated against a mercury U-tube
manometer  upon receipt and  every  quarter thereafter  or upon  erratic behavior.
Attach the the  absolute  pressure  gauge  and  mercury U-tube manometer  to  a "T"
connection  with a vacuum  pump.   Compare the readings at  atmospheric pressure.
Pull a vacuum  of 10  mm Hg of  absolute pressure.  Pressure  readings should agree
within 3 B™ Hg.  If  this criteria is not met,  make adjustments and repeat  the
calibration.

-------
Date








Reference
thermometer
type








Calibi
thermc
type



-




'ated
jcoupl«
use








i
no.








Anbier
refera








it teinpei
calibrb








Heasurec
-ature
differc








I values
Bo:
refer8








.ling wai
calibrb








;er
differc








Calibrator's
initials








                                                                                                         0
                                                                                                         01
                                                                                                             O
                                                                                                             p
                                                                                                             rt O
Temperature reading of the reference thermometer  in  °C  or °F.
Temperature reading of the thermocouple being  calibrated in °C or °F.
Difference between the reference thermometer and  the calibrated thermocouple.  This difference must
 be less than 3°C (5.4°F) for than initial  calibration  and 6°C (10.4°F)  for the calibration check.


                           Figure 2.4.  Thermocouple calibration form.
                                                                                                          O CD ft

                                                                                                            3 O
                                                                                                          000 3


                                                                                                            CO O
                                                                                                              CO
                                                                                                            I-* •
                                                                                                            VD H»
                                                                                                            VD-J
                                                                                                            I-' •
                                                                                                              rvj
O
                                                  O
O

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                                                         Section No. 3.1?.2
                                                         Date May 31. 1991
                                                         Page  9
               Table 2.1.   ACTIVITY MATRIX FOR  CALIBRATION OF EQUIPMENT
Apparatus
 Acceptance limits
Frequency and method
   of measurement
Action if
requirements
are not met
Sample tank volume
Within 5 g or 5 ml
 Calibrate initially
 and when not within
 10% of calculated
 volume or shows
 erratic behavior
Repair or
replace and
recalibrate
Sampling train
volume
No limits
 Calibrate initially
 as described in
 Section 2.1.2
Repeat
Rotameters
Y = 0.9 to 1.1 and
all Y  = Y +_ 0.5 Y
 Calibrated initially
 and when calculated
 volume not within 10%
 or erratic behavior
Repair, replace,
and recalibrate
Thermometers
Within 3°C {5.
of true value
 Calibrate initially
 as a separate com-
 ponent with mercury-
 in-glass thermometer;
 check before each
 test against mercury-
 in-glass thermometer
Adjust or replace
Barometer
Within 2.5 mm
(0.1 in.) Hg of
mercury-in-glass
barometer or weather
station value
 Calibrate initially
 using mercury-in-
 glass barometer;
 check before and
 after each test
Adjust to
agree with
certified
barometer
Absolute
Pressure
Gauge
Within 3 mm Hg of
mercury U-tube
manometer
 Calibrate initially
 using mercury U-tube
 manometer; repeat
 every quarter or
 upon erratic behavior
Adjust to
agree with
mercury
U-tube
manometer

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o
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                                                         Section No.  3.17-3
                                                         Date May 31,  1991
                                                         Page 1
3.0   PRESAMPLING OPERATIONS
      This  section addresses the preparation and packing of supplies  and  equipment
 needed for the sampling.   The pretest sampling checks  (Figure 3-1)  is a listing of
 equipment  pretest operational checks which should be completed before  leaving  for
 the field.   The pretest preparations form (Figure  3-2)  can be used as an equipment
 packing checklist.  The quality assurance activities for the presampling operations
 are summarized in Table 3-1 at the end of this section.

 3.1  Preliminary Survey

      The preliminary survey  may  be needed to  properly design the  final emission
 sampling  and  analytical protocol.    Preliminary   measurements  may include
 determining the stack dimensions,  the flue gas moisture,  stack pressure,  and stack
 temperature,  if the concentration of organics is  to be determined  on the basis of
 stack  conditions.    Other measurements  which  may  be  made,  depending  upon  the
 requirements  of the applicable regulation and the  source operations, include a flow
 rate determination, velocity check,  and  stack gas temperature range.   The  tester
 must determine  these requirements  and use the proper test methods  to  establish
 these data (i.e., EPA Methods 1 through 4).
      One of the primary concerns for any  organic  sampling program must be safety.
 The tester should  always  question  the facility representative concerning general
 plant safety  requirements  and safety in regard  to  sampling at the selected sampling
 site.    Every  sampling  and  analysis   protocol  should  address  the  safety
 considerations involved in performing  the protocol.   Because there are numerous
 safety considerations involved  in organic sampling,  it  is beyond the scope of this
 Handbook to discuss each one  in detail.  However,  it cannot be over-emphasized that
 the tester must always  be  aware of  the safety hazards.
      Figure 3-3 may be  used to collect preliminary survey data.

 3.2  Checking and Calibrating the Apparatus

 3.2.1   Sampling  System  -  The  Method  25 sampling   train  (see  Figure 1.1)  is
 commercially  available or  can  be manufactured  in-house if  the apparatus complies
 with  specifications  in  the  EPA  Test   Method  (see  Section  3.17.10).    These
 specifications and other  performance  criteria are discussed in  greater detail in
 Section 3•17•1•

      Heated Probe - The probe's thermocouple should have been initially  calibrated
 as  described in  Subsection 3.17.2.3.   Prior to each field  test, the thermocouple
 should be  attached  to  the temperature readout device  and  the probe thermocouple
 reading should  be  compared  with  a reference  thermometer  reading at  the ambient
 temperature.   If the values  are  not within 3°C (5.4°F) of  each  other,  replace or
 recalibrate the thermocouple.
      The probe should be cleaned with acetone  or  methylene.chloride, nitric acid,
 and distilled or deionized water.   To dry  the  probe, turn on the probe heater and
 purge the  probe with  UPC air  or nitrogen.   The objective is to leave  the  probe free
 of  contamination.
      Leak  check the probe  and check  the probe heater system as part of the complete
 train assembly as described below.

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                                                         Section No. 3.17-3
                                                         Date May 31, 1991
                                                         Page 2

Date 	   Calibrated by	

Heated Probe

Heater system capable of maintaining heat at probe exit at 129°C? 	 yes 	 no
Thermocouple calibrated against reference thermometer? 	 yes 	 no (within 3°C)
Probe cleaned with soap and water and acetone, then dried? 	 yes 	 no
Probe leak checked with sampling system? 	 yes  	 no

Filter Holder/Heating System

Heater system capable of maintaining heat at filter exit at 121°C? 	 yes 	 no
Thermocouple calibrated against reference thermometer? 	 yes 	 no (within 3°C)
Assembly cleaned with soap and water and acetone, then dried? 	 yes 	 no
Filter assembly leak checked with sampling system? 	 yes  	 no

Condensate Trap

Traps burned at 300°C until acceptable blank level achieved? 	 yes 	 no
Nitrogen placed in trap and trap sealed? 	 yes 	 no

Purge System

Rotameter initially calibrated? 	 yes  	 no (accuracy lOJt, precision 5%)
Purge system checked with sampling system and indicated flow? 	 yes 	 no

Sampling Rotameter

Initially calibrated against primary standard? 	 yes 	 no (accuracy 10%,
  precision 5%)
Calculated sample volume within 10% of actual sample for last test?
  	 yes 	 no

Sample Tank

Tank volume calibrated gravimetrically or volumetrically? 	 yes 	 no (+_ 5 ml)
Tank cleaned and filled with nitrogen? 	 yes 	 no

Barometer or Absolute Pressure Gauge

Calibrated against mercury-in-glass barometer? 	 yes 	 no
  (l 2.54 mm Hg)

Ambient Thermometer

Initially calibrated against reference thermometer? 	 yes 	 no (+_ 1°C)


                       Figure 3-1-  Pretest sampling checks.
o
o
                                                                                     o

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                                                         Section No.  3.17-3
                                                         Date May 31, 1991
                                                         Page 3
Apparatus check
Sampling System
Heated Probe
Heating checked
Thermocouple
calibrated*
Cleaned*
Leak checked
Filter Holder/Heater
Heater checked
Thermocouple
calibrated*
Cleaned*
Leak checked
Condensate Trap
Burned & blank
checked*
Sealed*
Purge System
Pulls flow
Sampling Eotameter
Calibrated or checked*
Sample Tanks
Calibrated*
Cleaned*
Pressure Gauge
Calibrated*
Ambient Thermometer
Calibrated or checked
Sampling Supplies
Dry ice
Fi Iters
Free of organic
binder*
Acceptable
Yes









No









Quantity
Required









Ready
Yes









No









Loaded and Packed
Yes









No









*Most significant items/parameters to be checked.

                        Figure 3^2.  Pretest preparations,

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                                                         Section No.  3.17-3
                                                         Date May 31.  1991
                                                         Page 4
I.  Name of company
    Address

    Contacts
                                                     Date_
                                                                           o
                                                     Phone
            Process to be sampled_
            Duct or vent to be sampled_
        II.  Process description_
            Raw material
            Products
Operating cycle
     Check:  Batch
                               Continuous
III.
                 Timing of batch or cycle
                 Best time to test
              Sampling site
              .   Description
                 Site description
                                                          Cyclic_
                 Duct shape and size_
                 Material
                                                                           O
Wall thickness
Upstream distance
Downstream distance

inches
inches
inches
diameter
diameter
Size of port
         Size of access
         Hazards
                                area
             B.
                                                 Ambient temp
     Properties of gas stream
     Temperature _ _°C
     Velocity
                                      F,
         Static pressure
         Moisture content
         Particulate content
         Gaseous components
                                                  Data source
                                                ,  Data source
                                      inches H20,  Data source
                                               %,  Data source
                                                ,  Data source
            N2
            02
            CO
            C02
            S0
                                 %  Hydrocarbons (ppm)    Toxics/Acids (ppm)
                                                          H2S
                                                          HC1
                                                          HF
                                                          Other
(Continued)
                    Figure 3-3-  Preliminary survey data sheet.
                                                                            O

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                                                        Section No. 3.17-3
                                                        Date May 31, 1991
                                                        Page 5
Figure 3-3 (Continued)

                    Hydrocarbon components
                                                           PPm
                                                           ppm
                                                           ppm
                                                           ppm
                                                           ppm
                                                           ppm
             C.   Sampling considerations
                 Location to set up sample recovery  area
                 Special hazards to be considered_
                 Power available at duct_
                 Power available for GC
                 Plant safety requirements_
                 Vehicle traffic rules
                 Plant entry requirements
                 Security agreements
                 Potential problems
                 Safety equipment (glasses,  hard hats,  shoes,  etc.)
             D.   Site diagrams.   (Attach additional sheets if required).

        IV.  On-site collection of preliminary survey samples
             A.   Evacuated tank
                 Tank have been cleaned, heated in furnace and purged
                 with nitrogen?	
                 Tank evacuated to the capacity of pump?  	
                 Filter end of probe placed at center of stack,  probe
                 purged and sampled collected into flask until flask is at
                 stack pressure?	
                 Stopcocks closed and taped?	
                 Duct temperature and pressure recorded?	
             B.
Purged flasks
Flasks cleaned and purged with nitrogen?	
Filter end of probe placed into stack, sample purged for
2 to 5 min and then stopcocks closed?	
Stopcocks taped to prevent leakage?	
                 Duct temperature and pressure recorded?	
                 Stability and adsorption checks conducted?
(Continued)


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                                                         Section No.  3.17-3
                                                         Date May 31,  1991           ^-s.
                                                         Page 6                      (   )

Figure 3.3  (Continued)

             C.  Quality assurance performance audit samples
                 Range of emissions to order proper range of performance
                 audit samples 	 inlet ppm 	 outlet ppm
                 Address to send audit samples 	
             D.   Bulk samples and screening techniques
                 Bulk emission sample(s)  collected?	
                 Bulk liquid sample(s)  collected?	
                 Detector tubes or other screening techniques used?_
             E.   Safety with respect to sample collection
                 Can gases be exhausted through purge system?  	 yes  	no
                 Can electrical service be used? 	 yes 	 no
                 Can heated probe and heated filter be used? 	 yes  	no
                 Can thermocouple be used?  	 yes 	  no

            F.   Emission results must be reported in terms of:
                    ppmC at standard conditions 	
                    ppmC at stack conditions	
                                                                2
ppmC at standard conditions corrected for CO
ppmv as a related solvent at standard conditions
ppmv as a related solvent at stack conditions
pounds per hour of carbon '	
o
                    pounds per hour of related solvent
                                                                                     O

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                                                         Section No. 3-17-3
                                                         Date May 31, 1991
                                                         Page 7

     Filter Holder  and Heating System - The  filter  holder assembly's thermocouple
should have been initially calibrated as described  in Subsection  3-1?.2.3.   Prior
to  each  field  test,  the thermocouple should be attached  to  the readout and the
probe thermocouple  reading  should  be  compared with  a reference thermometer reading
at  the  ambient  temperature.   If  the values  are  not within  3°C (5.4°F) of  each
other, replace or recalibrate the thermocouple.
     The filter holder/heating assembly should be cleaned with acetone or methylene
chloride, nitric acid, and distilled or deionized water.   To dry the filter holder,
turn on the probe heater and purge the filter holder with UPC air or nitrogen.   The
objective is to leave the assembly free of contamination.
     Leak check  the filter holder assembly and  check the filter  heater  system as
part of the complete train assembly as described below.

     Condensate  Trap - Before  its initial use  and  after  each subsequent use,  a
condensate trap  should be  thoroughly  cleaned and checked to insure  that  it  is not
contaminated.   Both cleaning  and  checking can  be  accomplished by  installing the
trap  in  the condensate  recovery system  and  heating to  300°C while performing  a
system background test (described in Section 3«17-5-2.1).  A trap may be considered
clean when its  effluent concentration is below  10  ppm.   Clean  or "blanked"  traps
should be filled with nitrogen and sealed to prevent contamination and corrosion.
If a trap cannot be properly "blanked," it should be discarded.  The history of the
trap  should  also be  tracked.    It is recommended  that  traps previously  used for
inlet sampling be used only for inlet sampling thereafter.

     Purge System -  The  purge  system  must  be  capable  of  purging the  probe and
filter holder assembly at  a rate of  60  to  100 cc/min.   Upon  initial receipt, the
rotameter should be calibrated as described in Section 3-17-2.   After  the initial
calibration,  the  rotameter  and pump should be checked prior to  each field test to
ensure that  it  is  capable of purging  the sampling system at  the  rate  indicated
above.  The  rotameter for the purge  pump is  used only as  a  flow indicator during
the field test.
     To  check   the  operations  of  the sampling  system,  the probe,  filter
holder/heating  assembly, and purge system should be assembled  in  the  same  manner
that it will be used in the field with the exception that  (1)  no filter is needed
and (2) the tank will not be attached.  Check the system as follows:
     1.  Turn on the probe and the filter holder heaters.
     2.  With the inlet to the probe open, turn the sample tank valve off, turn the
         purge pump  on,  set the flow rate to about  80 cc/min,  and allow  air to be
         drawn through the system until the operating temperatures are met.
     3.  After the probe and filter holder  comes to the  proper temperatures (probe
         129°C  and  filter  121°C),  plug the inlet to the probe  and  conduct  a leak
         check as described in Subsection 1.1.10.   If the system does not pass the
         leak check, repair or replace the  faulty component(s)  and repeat the leak
         check until it is acceptable.

     Sampling Eotameter -  The  sampling rotameter must be  calibrated (1)  initially
as described in Subsection 2.1.3,  (2) when  the posttest  calculated volume from the
previous field  test is not  within 10% of the actual sample volume  collected and
(3)  any  time  the  rotameter  exhibits  erratic  behavior.    If  the  rotameter  is
acceptable using the criteria above,  the tester may attach the purge pump after the
sample tank valve and ensure that the rotameter does not  exhibit erratic behavior
by pulling  a flow  of  about  80 cc/min.   If erratic behavior  is exhibited,  the
rotameter should be cleaned and recalibrated.
                                                    •it'

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                                                         Section No.  3-17.3
                                                         Date May 31.  1991           ^-^
                                                         Page 8                     f   )

     Sample Tanks -  Each sample tank must be initially calibrated as described  in
Section 3.17.2.  After the initial calibration,  it should be visually checked prior
to each  field  test  to ensure that there  are  no dents that would effect the total
sample volume.   Each  tank must also  be  flushed with  UPC air  until  there is  no
response on the NMO  analyzer.   After a tank is  free  of hydrocarbon  contamination,
it should be evacuated and filled with nitrogen to a pressure  of approximately  10
mm Hg above atmosphere.  The nitrogen will prevent contamination and  corrosion.

     Mercury Manometer or Absolute Pressure Gauge - If a mercury manometer  is used,
then  a barometer will be  required.    No calibration  is required  for a  mercury
manometer.  The manometer or absolute pressure gauge should be leak checked as part
of the assembly as  described above.   The barometer and/or  absolute  pressure gauge
should  be  calibrated  against a  mercury-in-glass  barometer  as   described  in
Subsection  3.17.2.4.   If  it  does  not  agree  within  2.54 mm  Hg,   it should  be
corrected or replaced.

     Thermometer for Ambient Temperature  - A thermometer is needed  to  measure  the
ambient  temperature.   If the thermometer is a  mercury-in-glass  thermometer with a
sensitivity of 1°F,  the thermometer should be initially check against a mercury-in-
glass  ASTM  thermometer  as described  in  Section  3-17.2.    After  the  initial
calibration, the  thermometer should  only  be visually checked to  ensure that it  is
not  broken.    If  a  thermocouple  is  used to measure  the ambient temperature,  it
should be checked at ambient temperature against a reference thermometer and should
agree with 1°C.
3.2.2  Sampling Supplies - The following supplies are needed for sampling:

     Crushed Dry Ice - Crushed dry ice is needed to cool the condensate trap during
sampling  for  better collection  of organics  and to keep  it cool until  analysis.
There is no specification on the dry ice.

     Filters  -  Glass fiber  filters,  without organic binder are needed to  remove
organic   particulate  matter  from  the  gas  stream  during  sample  collection.
Typically,  the  filters  used for  EPA  Method 5  sampling  are  satisfactory,  if  no
organic binders are present.  If organic binders are present,  they may be  released
during testing and positively bias the results.   If the tester is not certain about
the presence  of organic  binders  in a glass fiber filter,  it should  be placed  in a
furnace  at 300°C for  2  hours  to  remove  any  organic  binders  present.    This
procedure, however,  may  make the  filter more brittle  resulting in  a  greater  need
for caution  in handling.   A check  on  the  amount of  organic binder lost  during
heating  can  be  determined by  following  the  procedures  described  in  Subsection
1.3.1.

3-3  Packing the Equipment for Shipment

     The  sampling system  is relatively small,  made  predominately of  stainless
steel, and therefore  rugged with the  exception of  the  rotameters,  pumps,  and
pressure gauges.  The filter holder system and probe may be packed separately or as
a  unit.    The  other components  should be  packed  conveniently  and  securely  in
labeled  containers   (as  to  contents)  for ease   of  identification  in the  field.
Polyethylene foam can be used to cushion the  components.  Also, the tanks should be
secured so they do not become dented.
                                                         .1
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                                         Section No.  3.17.3
                                         Date May 31, 1991
                                         Page 9
Table 3.1.  ACTIVITY MATRIX FOR PRESAMPLING PREPARATION

Operation
Apparatus
Check and
Calibration
Heated probe
Filter holder
Condensate
trap
Purge system
Rotameter
Sample tank
Pressure
gauge
Sampling
Supplies
Dry ice
Filters
Packing Equip-
ment for Ship-
ment


Acceptance limits
Leak free, cleaned,
capable of heating
to 129° C with cali-
brated thermocouple
Leak free, cleaned,
capable of heating
to 121° C with cali-
brated thermocouple
Acceptable blank
level
Capable of purging
at rate of 80 cc/min
Calibrated
Volume calibrated
to +_ 5 ffll and
clean
Range 0 to 900 mm
Hg within 2.5^ mm Hg
No specifications
Glass fiber with
no organic binders
Packed in secure
container

Frequency and method
of measurement
Clean with soap and
water, then acetone;
calibrate thermocouple
against reference
thermometer; conduct
heater check and leak
check with assembly
As above
Check as described in
Subsection 3.17.5, 	
Check as part of
sampling assembly
Calibrate as shown
in Section 3.17.2
Calibrate and clean
as described in
Subsection 3.17.1.1
Check against mercury-
in-glass barometer
Not applicable
Check or heat filter
Before field trip,
pack in shipping
container

Action if require-
ments are not met
Repeat cleaning,
calibration, and/or
heater and leak
checks
As above
Repeat burnout and
repeat blank check
or replace and repeat
Repair and repeat
Clean and recalibrate
Recalibrate and/or
reclean
Adjust and repeat
calibration
Not applicable
Replace
Repack

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                                                            Section No. S.I?.1
                                                            Date May 31. 1991
                                                            Page 1
4.0   ON-SITE MEASUREMENTS
      On-site  activities  include  transporting  the  equipment  to the  test  site,
 unpacking and  assembling the  equipment,  sampling  for  total gaseous  nonmethane
 organics,  and recording the  data.   The associated quality assurance  activities are
 summarized in Table 4.1 at the end of this section.

 4.1   Transport of Equipment to the Sampling Site

      The  most efficient means of  transporting  the equipment from ground  level  to
 the   sampling site   (often  above  ground  level) should be  decided  during  the
 preliminary  site  visit or  by  prior  correspondence.    Care  should be  taken  to
 prevent damage  to  the equipment or injury to test personnel during  the moving.   A
 clean "laboratory"  type area free  of  excessive dust and organic  compounds  should
 be  located and designated for preparing  the  tanks,  traps,  and filter holder,  and
 for  sample recovery.

 4.2   Preliminary Measurements and Setup

      It is recommended that a preliminary survey be conducted prior to sampling and
 analysis,  unless adequate  prior  knowledge  of  the  source  and/or information, is
 available.  Testing  must be conducted at the proper sampling  locations and  during
 the  proper process  and control equipment operating cycles or periods.  The  tester
 should  refer  to Subsection  3«17«3«1  regarding the  information that is  typically
 needed  to establish  the  proper  sampling and analysis  protocol.   The accuracy  of
 sampling  and  analysis following  handling  and  transportation  of the sampling  system
 to and from the sampling site is determined using a cylinder gas audit.
      One  of the  primary concerns for any organic sampling program must be safety.
 The  tester should always question the facility  representative concerning general
 plant safety  requirements and safety in regard to sampling at the selected sampling
 site.   Every  sampling and analysis protocol  should address the  safety  considera-
 tions involved in  performing the  protocol.    Because there  are numerous  safety
 considerations  involved  in  organic  sampling,   it is  beyond  the  scope  of  this
 Handbook  to discuss each one in detail.  However, it cannot be over-emphasized that
 the  tester must always be aware of the safety hazards.

 4.3   Sampling

      Because  of  the unlimited  variations  in  sampling organic  compounds  from
 potential  source  types,  only the  more  general  common situations and problems are
 addressed  in  this section.  Both required and recommended quality assurance/control
 checks  and procedures  are  provided  to  assist  in  the  collection  of  acceptable
 quality data  and to assess the accuracy of the sampling and analysis.
      On-site  sampling includes the following steps:
      1.  Conducting preliminary measurements and setup of the recovery area.
      2.  Preparation  and setup of the sampling system.
      3.  Connection of electrical service and leak check of the sampling system.
      4.  Heating the  probe and filter to proper temperature.
      5.  Insertion of the probe into the duct and sealing the duct.
      6.  Purging of the sampling system.
     7-  Constant rate sampling.
     8.  Recording data.
                                                       /•
                                                       (-I

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                                                            Section No.  3.1?.4
                                                            Date May 31,  1991
                                                            Page 2

     9.  Recovering the sample and its transportation to the laboratory.

4.3.1   Preliminary Measurements and  Setup of Recovery  Area - All  test  personnel
should be knowledgeable of the plant safety requirements.  This includes areas that
should  not be  entered and  whether  the  plant will  allow  the  use of  electrical
service in the sample  collection  area.    The  risk to  test personnel  of being  in
process areas handling  organic  compounds,  removing gases from these processes,  and
venting sample gases into the sample collection area may be significant.   The  plant
may require that no electrical service be used and/or that the sample gases  removed
from the process during the pretest purging of the sampling system be adsorbed onto
some vehicle such as a resin or charcoal or vented back into the process.
     After  all  testing personnel are  familiar with plant  safety  requirements  and
all potential  safety hazards, preliminary measurements  and setup may begin.   The
sampling  site  should  be  checked  to  ensure  that  adequate electrical service  is
available  (if  allowed).    The  stack dimensions  are  measured and recorded  (if
applicable) on  a field sampling data sheet such  as  the one shown  if Figure 4.1.
If the  concentration of the organics are to be determined  on any  basis  other than
ppmC at standard conditions, the corresponding preliminary measurements  should  be
made at this time.   Moisture content  of  the stack cannot be measured by Method 25.
Therefore,  if  the  final   emissions are to  be  presented in  terms  of  stack
concentration or mass emission rate, or are to be corrected to a C02 concentration,
or to an equivalent  solvent  basis,  Methods 1  through 4  will most likely need  to be
conducted simultaneously with Method  25 •   Prior to final sampling,  the tester must
determine on what basis the final results are to presented.
     If the emissions are to be presented in terms  of  a mass emission  rate,  the
flow rate of the stack gas, including its moisture content, must be determined.   In
this case,  it  is preferable  that  the sampling location be  selected in  accordance
with Method 1  (or Method 1A,  if applicable).   If  this is impractical,  it should be
selected  to minimize  flow  disturbances.   The  number  and locations  of  sampling
points for  the velocity traverse are  selected according to Method  1  (see  Section
3.0:1  of  this  Handbook);  the  traverse  is  conducted according to  Method 2 (see
Section 3.1 of this  Handbook).   Note; The  Method 25  sampling  is  conducted at a
single  point  of  average   velocity.    If  it  is  unsafe  to  conduct a  preliminary
velocity traverse or a traverse is not required,  the sampling may be  conducted at
the center  of  the  duct or at a point at least 3 feet into  the  duct (whichever is
less).   The port must be sealed well  and there must be no  reason  to  suspect that
the emission concentration is not uniform across the stack.
     Method 25  requires constant rate sampling;  the sampling rate  is  not  changed
with regard to the flue gas  flow rate.   However,  if the emissions are  presented on
a mass emission  basis,  the flue gas flow  rate must be  measured  during each Method
25 sample  run  and  the corresponding flow rate used  to  determine the mass emission
rate for that run.
     Select a  total  sampling time  greater than  or equal to the  minimum sampling
time specified in the applicable  subpart of the  regulation or  other  applicable
emission standard.  The data will be recorded at 5-minute intervals.
     A clean "laboratory"  type area should be found to load the filter, recover the
samples, conduct orsat analyses,  prepare and recover the  moisture sampling train,
and to store other sampling  equipment.   This  area should be free of excess  dust or
high levels of organics.   Because  of the relatively small size of the  Method 25
sampling equipment and  the nature of  Method 25 sample recovery,  the stack location
can often be used as the recovery area.
o
o
 o
                                                 .(i

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                                                            Section  No.  3.17-4
                                                            Date  May 31.  1991
                                                            Page  3
Company Name
Address 	
           Run No.
           Date
Sampling Location 	;	  Start Time _
Tank No. 	 Trap No. 	 Sampling Train No.  	  Finish Time
Thermocouple No. 	   Barometer No.  	        Operator 	
Vacuum Gauge No. 	
Tank Volume    	   liters                    Train Volume 	
                             cc
Calculated Allowable Change   p
cm Hg
                                  TANK PARAMETERS
Parameter
Pretest
Posttest
Barometric
Pressure
in. Hg


mm Hg


Tank
Temp.
op


°C


Final Pressure
Tank Pressure
mm Hg
Gauge



Absolute



Leak Check
(cm Hg/min)
Tank

System


                                    SAMPLE DATA
Clock Time













Tank Vacuum or
Gauge Pressure,
in. Hg (mm Hg)













Flow Meter
Setting, cc/min













Sample Gas Temp., °F (°C)
Probe Exit













Filter Inlet













                      Figure U.I.  Field sampling data  form.

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                                                            Section No.  3.1?.4
                                                            Date Hay 31, 1991        ^-^
                                                            Page 4                  f   J

4.3.2  Sampling System Preparation - Sampling  system  preparation includes  (1) leak
checking the  tanks,  (2)  assembling the sampling  train,  and (3)  leak checking the
entire sampling system.   This preparation should be conducted as follows:
     1.  The  sample  tanks  should  be  evaluated   to  10  mm  Hg  or less  absolute
         pressure.  The  pressure  must  be measured with a mercury U-tube manometer
         or absolute pressure gauge capable of measurement  within 1 mm  Hg.   Record
         the tank pressure  on  the field sampling data form  (Figure 4.1 or similar
         form).    Close   the  sample tank  valve and allow  the  tank to  sit  for  60
         minutes.   The  tank  pressure  should  then  be  rechecked  using the same
         pressure  gauge   and  this  pressure recorded.    If  after  60  minutes  no
         noticeable change  (less  than  4 mm Hg) has occurred in the tank pressure,
         the tank  is  acceptable for testing.   The tank evacuation  and leak check
         may be conducted either in the laboratory or the field.
     2.  Just before  sampling  train assembly,  measure the  tank  vacuum  using  a
         mercury U-tube manometer or absolute pressure gauge capable of measurement
         to within 1 mm Hg.  Record this pressure, the ambient temperature, and the
         current barometric pressure on the field sampling data form.
     3.  Close the  sample  tank valve and assemble the sampling system  as  shown in
         Figure 1.1.
     4.  Immerse the  condensate trap body in  dry ice.   The point  where the inlet
         tube joins the  trap  body should be 2.5  to 5 cm above  the top of the dry
         ice.
     5.  After assembling the sampling  train,  plug the probe  tip, and make certain
         that the sample tank valve is closed.                                        /"""N
     6.  Turn on  the  purge  vacuum pump, and evacuate the sampling  system  from the  (    j
         probe tip to the sample  tank valve  to an absolute  pressure of 10 mm Hg or  ^—
         less and record the pressure on the field sampling data form.
     7.  Close the purge valve, turn off  the pump,  wait  5 minutes,  and recheck the
         indicated pressure and record this reading.   The  change  in  the  absolute
         pressure of  the tank  during  the  5-min  period is the  measured  pressure
         change  (delta   P).    Note;  A less  sensitive  pressure gauge,  which  is
         standard on  commercially available equipment  and  reads pressure  to the
         nearest  0.5  in.  Hg,   can  be  used  for  indication of  the vacuum  during
         testing, but cannot  be used for measuring the  tank pressure  and  for the
         leak check procedure.   The tester must conduct the  leak check by attaching
         the mercury U-tube manometer or pressure gauge at the probe inlet.
         The sample tank must remain closed.   If opened,  the extremely large volume
         of the  tank  compared  to  the  sample system  makes  detecting a small leak
         extremely difficult.
     8.  Calculate the maximum  allowable pressure  change based  on a leak rate of 1
         percent of the  sampling  rate  using the equation below.  Record it on the
         field sampling  data form.   This should  be compared  to the  measured   P
         from Step  7 which must  be  less  than  or  equal  to  the  allowable     P
         calculated in Equation 4-1.
                     P = 0.01 FPb9                                        Eq. 4-1
                               vt
         Where:
                P = Allowable change, cm Hg,
                F = Sampling flow rate, cc/min,
               Pb = Barometric pressure, cm Hg,
                8 = Leak check period, min, and
               Vt = Sampling train volume from probe tip to tank volume, cc.
                                                 •J/
o

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                                                            Section No.  3.17.4
                                                            Date May 31,  1991
                                                            Page 5

     9.  If the measured pressure change exceeds the calculated limit,  correct the
         problem before beginning sampling.
    10.  Mark the probe such that when placed in the stack,  the nozzle will be  at a
         point of average velocity.  Alternatively, if the  flow cannot  be measured
         or does not have to be measured, mark  the  probe  such that the  nozzle  will
         be placed at  the  center of the duct or a  point  at least  three  feet  into
         the duct (whichever is less).
     11. Calculate  the sampling rate  for  the test  by dividing  sampling  time
         (minutes) into 80% of  the  sample  tank volume (cc).   The  resulting  flow
         rate, in cc/min,  will be used for the testing and will provide  a margin of
         error.
     12. Complete all remaining entries on the field sampling data form  that can be
         completed prior to the start of the test run.  This includes all facility,
         sampling  train  component,  and  run  information  plus  the  barometric
         pressure.

4.3.3   Constant  Rate Sampling - Sampling must  be  conducted at a  constant rate (+_
10%) over  the duration of the  sampling  period at a  rate of  between  60  and 100
cc/min.  Follow the steps below to obtain a constant rate  sample:
     1.  Unplug  the  probe  tip, and  place  the probe into the stack such  that the
         probe is  perpendicular to the duct  or stack axis  and the probe tip (or
         nozzle)  is located at a point of average velocity with the tip  facing away
         opposite of the direction  of  gas  flow.  For ducts with a negative static
         pressure, sufficiently  seal the sampling  port  to prevent  air in-leakage
         around the probe.
     2.  Set  the probe  temperature controller  to 129°C (265°F)  and  the  filter
         temperature controller  to  121°C  (250°F).   Allow the probe and  filter to
         heat for about 30 minutes prior to purging the train.
     3.  To purge  the  probe and filter assembly,  close the sample  valve,  open the
         purge valve, and start the vacuum pump.  Set  the flow rate between 60 and
         100 cc/min,  and purge the train with sample gas for at least 10 minutes.
     4.  When the temperatures at the exit ends of  the probe  and filter are within
         their specified ranges, sampling may begin.
     5.  Check the dry ice level around the  condensate trap, and add dry ice,  if
         necessary.
     6.  To begin  sampling,  close  the purge valve  and stop the pump.  Record the
         start time.    Open  the sample  valve and the sample tank valve.   Using the
         flow  control  valve,  set  the flow  through  the  sampling train to  the
         calculated flow rate.   Record the tank vacuum,  flow  rate  setting, probe
         temperature, and filter temperature.
     7.  Adjust  the  flow  rate  as  necessary  to  maintain  a constant rate •(+_  10%)
         throughout the sampling period.   Also, adjust  the probe  and  temperature
         controllers  as necessary to maintain the proper temperatures.
     8.  Record the sample  tank vacuum, flowmeter settings, probe temperature, and
         filter temperature at 5~°inute intervals.
     9-  Sample collection ends when the total sampling time is reached  or when the
         constant flow rate can no longer be maintained due to reduced  sample  tank
         vacuum.    If  sampling must  be interrupted  before  reaching the  minimum
         sampling time (specified in the applicable regulation)  because a constant
         flow rate cannot  be  maintained, proceed  as follows:   Record the  sample
         tank pressure  and temperature, close  the  sample  tank valve,  remove the
         used sample  tank  from the  sampling train  (without  disconnecting other
         parts of  the  sampling  train).   Take  another evacuated  and leak-checked

-------
                                                            Section No.  3.17-4
                                                            Date May 31,  1991
                                                            Page 6                /"""N

         sample tank,  measure  and record the new  tank vacuum,  and attach  the  new
         tank  to  the  sampling  train.    After  the  new tank  is  attached  to  the
         sampling train, proceed with sampling until  the required minimum sampling
         time has been reached.
     10. After sampling is completed, close the flow  control valve,  and  record  the
         final tank  vacuum;  then  record the tank  temperature  and  the  barometric
         pressure.  Close the sample tank valve.
     The sampling train will be recovered as described below.   After the trap  and
tank are disconnected from the sampling train, both the Sampling System  Preparation
procedure  (steps  1  through 12)  and  Constant  Rate  Sampling  procedure (steps  1
through 10)  are  repeated for  the  next  sample run.   If the tester  feels  that  the
filter  will  not become  plugged during  the  subsequent sample  run,  the  probe  and
filter  holder/filter  assembly including  the used  filter  may  be used for  any
proceeding sample runs.
     A  cylinder  gas  performance  audit  shall  be  conducted  during  the  sample
collection phase of  the  test.   The procedures for  collecting the cylinder  gas  are
described in Section 3-17«8«  Method 25 requires that each test  be audited with  two
concentrations of cylinder gases.  Since the  tester must have two sampling trains,
a regulator,  connecting tubing, and a  sampling  manifold available  for  the audit,
these items  must  be included  in the test protocol.   The  collection of  the audit
gases should  be  conducted in  the same  manner as  collection of  the  field  samples
with the exception that the probe, filter holder,  and purge system are not used  for
collection of  the audit gases.   If the  agency representative  is not present at  the
start of field sampling,  the  tester should wait until  the  conclusion of the field
test  to  conduct  the  audit;  it  is  always  preferable  to  have  the
representative present during  the  audit.  The tester should not  break  the  seal
the audit cylinders until just prior to collecting the audit samples to  provide  the
agency with the maximum  opportunity to observe  all steps in the collection of  the
field samples and the audit samples.

4.3.4  Sample  Recovery -  Prior to sample recovery, the flow control valve  and  the
sample  tank  valve should  be  closed  and the field sampling data form  should be
completed.     If   the  sampling location  is  not   suitable  for  conducting  sample
recovery,   the sampling  train  should  be removed  to  the sample recovery  area;
otherwise,  the sample  may be  recovered  at  the  sampling location.   Samples should
be recovered as follows:
     1.   Disconnect  the  sample  tank  from  the  sampling  system.   If  the less
         sensitive pressure  gauge  (see Note  in  Subsection  4.3.2)  was used  for
         sampling, the  tank  should be  immediately attached to  the  more sensitive
         gauge (reading to within 1 mm Hg) and the tank pressure recorded.
     2.   Disconnect  the  condensate trap  at  the flowmetering system, and  tightly
         seal both ends of  the trap.   The probe (from the stack  to  the  filter) is
         not included as part of the condensate  sample.
     3-   Pack the trap in dry ice during storage  and shipping and until  the samples
         are analyzed.
     4.   Ensure that  the  condensate  trap and  the  sample tank(s)  are  properly
         identified by the  test run number and their corresponding identification
         numbers  are properly entered on the  field  sampling data  form.   The use of
         a  standardized label  is  encouraged  and  is helpful in  ensuring  consistent
         identification by the laboratory staff.                                    x—N
     5.   Label a clean  condensate  trap and tank as sample blanks.  These  will be(    )
         analyzed  in  the  same  manner  as  the  field  samples   and then  used  tox	J
         determine the blank level of the sampling system.

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                                                            Section No.  3.17-4
                                                            Date May 31,  1991
                                                            Page 7
4.4  Sampling Problems
     Because  of the  large number  and variety  of organic  processes,  it  is  not
possible to discuss all the sampling problems related to Method  25  sampling.   Only
the  seven  most common  problems will  be  addressed:  (1) high  sample gas moisture
content  and  freezing of  the  trap,  (2) no use of electrical  service in sampling
area,  (3)  conversion  of C02  to a carbonate  in  the  trap,  (4) use of Method  25 for
measuring  low  levels of  organics,   (5)  sample  contamination,   (6)  sampling  and
analysis by  different companies,  and  (7)  measurement  in ducts  containing  organic
droplets.

4.4.1  High  Gas Sample Moisture Content and Freezing of  Trap - If  the  sample gas
has  a high  moisture content, the  small  line  running  from  the  filter  to  the
condensate trap tends to  freeze and the moisture blocks the sample  gas  flow.   For
this reason, the trap should clear the dry ice by 2.5 to 5  cm.   If freezing of the
moisture in  the line continues  to  be a  problem,  the line may  be  insulated to
improve  heat  transfer.   If the problem persists  and sampling cannot be conducted,
the  tester may place a "preliminary"  trap  in  front of the "primary"  trap.   The
"primary"  trap  should be placed in an ice bath  and the second  trap placed  in the
dry  ice  bath.   After  sample   recovery, both  traps are  placed  in dry  ice until
analysis.

4.4.2  Use Electrical Service  Not Permitted for  Probe and  Filter Heating -  If, for
safety  reasons, the  plant  cannot  allow  the  use  of  electrical  service   at the
sampling site,  sampling should be conducted using an in-stack  filter.   The filter
should consist  of  a  stainless  steel  tube  packed with quartz wool,  similar  to the
sampling filter in  the original version  of Method  25.    The  condensate  trap is
connected  directly  to the in-stack  filter,  and the sampling system is not purged.
Recovery  of  the  condensate   trap  does not include  the  in-stack  filter.    The
condensate trap must  comply with the revised Method 25 specifications.
                  '...-'-. t i .
4.4.3  Conversion  of C02  to Carbonate in  Trap  - It has been demonstrated  that if
ammonia  is  present  in  the duct during  testing,   the C02  can  be  converted to
carbonate  during  testing.   This  conversion results  in  a high  bias  during the
analysis of  the trap.   If this problem occurs,  consult the Administrator  for an
alternative procedure.

4.4.4  Use of Method 25 for Measuring Low Levels of Organics  -  Method 25  was not
intended to measure organics at levels below 50  ppmC.  However,  if the tester has
no other options.  Method 25 can be used under the following conditions:  (1)  extreme
caution  must  be used in preparing  the traps and tanks and (2) two  traps  and two
tanks should  be set  aside as  field  blanks with  the analytical  results subtracted
from the field sample  values.   This  approach  will  improve measurements at lower
level sources, although the precision  and accuracy of the method will be poor.

4.4.5  Sample  Contamination  -  Sample  contamination is  a major  problem with Method
25 sampling and analysis.  Precautions to prevent contamination are listed below:
     1.  Pretest preparation of the  probe, filter holder,  traps,  and  tanks cannot
         be overemphasized.  The  probe and  filter holder assembly  must be  cleaned
         in the manner  prescribed to eliminate organic materials.   The traps must
         be burned  after analysis  to remove any organics.   The traps  should be
         filled with  nitrogen  under  pressure and their history  should be tracked.
         It  is recommended  that no   trap  previously   used  for  sampling at  high

-------
                                                            Section No. 3-1?.4
                                                            Date May 31, 1991
                                                            Page 8

         organic levels be used for sampling extremely low levels of organics.
     2.  All components  of the train should  be maintained such  that  the surfaces
         are never  exposed  to organics  (e.g.,  oil  or  other organic compounds),
         particularly the quick-connects or fittings.
     3.  All  other   components,  such  as  the  tubing used  to  connect the  audit
         cylinders to the sampling manifold, must be free of organics.

4.4.6  Sampling  and  Analysts by Different Companies  - Because of the  small number
of laboratories  that  conduct Method 25 analysis, a large portion of the Method 25
sampling and analysis  is conducted by two different  companies  (i.e.,  the sampling
company  and  the analytical laboratory).    This  creates  problems  in  assigning
responsibility when  audit  sample results  are not  acceptable.    If  the  sampling
company wants  to check the  consistency  of the analytical  results (especially for
low level  organic sampling),  the  tester should  obtain  extra traps and cylinders
from  the  analytical laboratory.   These  clean traps and  cylinders should  not be
opened, marked as if they  were  a  sample,  and  submitted  for analysis with the field
samples.

4.4.7  Measurement in Ducts Containing Organic Droplets - If organic droplets exist
in the duct to be sampled, the Method 25 results can be greatly biased.  The tester
should first try to find another location where the droplets do not exist.  If this
is not possible,  two filters may need to be  placed in the system with both being
replaced after each  sample  run.   The addition  of  an in-stack  filter should help
collect organic  droplets  and will reduce the  loading on  the  out-of-stack (second)
filter.

4.5  Sample Logistics and Packing Equipment

     The sampling and sample  recovery procedures are followed  until  the required
number of  (1)  runs  are completed,  (2)  audit  samples are collected, and (3) blank
samples are labeled.   Log  all data on the sample recovery and integrity data form,
Figure 4.2.  At the conclusion of the test:
     1.  Check all traps and tanks for proper labeling (time, date, location, test
         run number,  and any other pertinent  documentation).  Be sure that blanks
         have been set aside  and labeled.
     2.  If possible,  make a copy of the field data  form(s)  in  case the originals
         are lost.
     3.  Examine  all  tanks  and traps  for damage  and  ensure  that the  traps are
         packed  in   a sufficient  amount  of   dry  ice for  transport  to  the base
         laboratory.   Ensure that  the containers are labeled properly for shipping
         to prevent loss of  samples or equipment.
     4.  Review  the  field  sampling data  form  and any other completed data forms to
         ensure that all data have been recorded and  that all forms are present.
o
o

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Plant Name  	
Sample Recovery Person
Plant Location
                                                 RECOVERED SAMPLES
Run
No.










Sample Type
Inlet Outlet Audit Blank










Trap
No.










Placed on
Dry Ice










Tank
No.










Date
Recovered










Time
Recovered










Remarks










                                                 LABORATORY CUSTODY
Date of Laboratory Custody
All traps still on dry ice?
Remarks
    Laboratory Person Taking Custody
    All samples identifiable?	
                               Figure ^.2.  Sample recovery and integrity data form.
                                                                                                                    LO C
                                                                                                                     H* •
                                                                                                                    *
                                                                                                                       «J
                                                                                                                     H* •

                                                                                                                    vo-
                                                                                                                     H1 •
                                                                                                                       J

-------
                                                           Section No. 3-17.4
                                                           Date May  31,  1991
                                                           Page 10
                 Table 4.1.  ACTIVITY MATRIX FOR ON-SITE MEASUREMENTS
                                                              o
    Characteristic
    Preliminary
    determinations
    and
    measurements
    Sampling
    system pre-
    paration
(Continued)
Acceptance limits
If final results on
stack concentration
basis, determine the
moisture content of
stack gas

If final results on
emission rate basis,
determine moisture
content and flow
rate of stack gas
                    Determine stack
                    dimensions

                    Select sampling
                    time y minimum   ,
                    total 'sampling time
                    in applicable!
                    emission standard;
                    number of minutes
                    between readings
                    shouldjbe an integer
Leak check tanks,
measure pressure
with manometer or
absolute pressure
gauge to within
1 mm Hg       :

Assemble sample
train as shown in
Figure 1.1

Mark the probe such
that nozzle will
be at the point of
average velocity; if
flow can not or
does not need to be
be measured, place
nozzle in center or
or 3 feet into duct
Frequency and method
   of measurement
Once each field test;
use wet bulb/dry bulb
thermometer, Method
4, or sling psychro-
meter

See above for
moisture content;
for flow rate, once
each field test using
Method 1 location,
if possible, and
Method 2 procedures

Prior to sampling,
using tape measure

Prior to sampling
Prior to sampling
                                           Prior to sampling,
                                           inspect all
                                           connections

                                           Prior to sampling,
                                           determine using
                                           stack dimensions
Action if require-
ments are not met
Complete
                                                                  Complete
                                              Complete
                                              Complete
                O
Repair or replace
if leaks found
                       Check for leaks,
                       repair system;
                       repeat check

                       Reposition
                                                                                  O

-------
Table 4.1 (Continued)
                                                            Section No.  3-17.4
                                                            Date May 31, 1991
                                                            Page 11
Characteristic
 Acceptance limits
Frequency and method
   of measurement
Action of require-
ments are not met
Sampling system
preparation
(continued)
Assemble system as
shown in Figure
1.1; no leakage
                  Check dry ice
                  level, and add
                  ice, if necessary

                  Close the purge
                  valve and stop
                  the pump; record
                  start time, open
                  sample valve and
                  sample tank, set
                  flow to calculated
                  flow rate and
                  record the tank
                  volume, flow rate
                  setting, probe
                  temp and filter
                  temp

                  Adjust flow rate
                  to maintain a
                  constant rate and
                  adjust probe and
                  temp controllers
                  as necessary to
                  maintain proper
                  temperatures

                  Record sample
                  tank vacuum, flow
                  meter settings,
                  probe temp and
                  filter temp at
                  5-min intervals
                  throughout sampling

                  Calculate sampling
                  rate for the test
Before sample collect-
ion visually and
physically inspect all
connections

Prior to sampling
                      To begin sampling
 Check for leaks;
 repair system;
 repeat check
                                              Complete
                        Complete
                      During sampling;
                      flow rate should
                      be kept at +_ 10%
                      throughout the
                      sampling period
                      During sampling
                        Repeat sampling
                        Complete
(Continued)
                      Prior to sampling;
                      divide sampling
                      time (min)  into 80%
                      of the sample tank
                      volume (cc)
                        Complete
                                                  /  XI  ,f
                                                 '' V<" '

-------
                                                            Section No.  3-17.4
                                                            Date May 31,  1991
                                                            Page 12
Table
            (Continued)
                                                                                  o
Characteristic
Constant rate
sampling
  (Continued)
                 Acceptance limits
                Adjust probe tip
                such that probe is
                perpendicular to
                stack axis- or nozzle
                is located at a
                point of average
                velocity with tip
                facing opposite of
                direction of gas
                flow

                Set probe temp to
                129°C; set filter
                temp controller to
                121°C allow probe
                and filter to heat
                for 30 min

                Purge train, close
                sample valve, open
                purge valve, and
                start vacuum pump

                To begin sampling,
                close purge valve
                and stop pump; open
                sample valve and
                sample tank valve

                Sampling must be
                conducted at a
                constant rate of
                i 10% over duration
                at a rate between
                60 and 100 cc/min

                Sample collection
                ends when total
                sampling time is
                complete or constant
                flow rate can no
                longer be maintained
                due to reduced
                sample tank volume
Frequency and method
   of measurement
Prior to sampling
                                        Prior to purging the
                                        train;  confirm using
                                        thermocouples
                                        Before sample
                                        collection,  with
                                        sample valve closed
                                        During field test
                                        During field test
                                        During field test
Action of require-
ments are not met
 Reposition; check
 system for leaks
                        Adjust heating
                        system
                        Repeat purge
                        Repeat sampling
                      O
                        Repeat sampling
                        If sampling must be
                        interrupted before
                        reaching the
                        minimum sampling
                        time, see
                        Subsection 4.3.3,
                        Step 9
                      O

-------
Table 4.1  (Continued)
                                                            Section No.  3-17.4
                                                            Date May 31, 1991
                                                            Page 13
Characteristic
  Acceptance  limits
Frequency and method
   of measurement
Action of require-
ments are not met
Constant rate
sampling
(continued)
After  sampling is
completed, close
the  flow  control
valve; record final
tank vacuum and
temperature, and
barometric pressure;
close  sample tank
valve

Conduct cylinder gas
performance audit
during sample
collection phase of
test
Immediately following
sampling
 Complete
                                        Collect two audit
                                        sample gas concentra-
                                        tions per test; see
                                        Section 3.1?.8
                        Complete
Sample recovery
(Continued)
Disconnect sample
sample tank from
sampling system;
record tank pressure
within 1 mm Hg

Disconnect
condensate trap;
seal both ends
tightly

Identify condensate
trap and sample
tanks by their test
run number and
sampling location
and enter corres-
ponding information
on field data form

Pack trap samples
in dry ice during
storage and
shipping

Label clean sample
tank and condensate
as sample blanks
Following sampling
 Complete
                                        Following sampling
                                        Following sampling
                        Complete
                        Complete
                                        Following sample
                                        recovery
                                        Following sampling
                        Complete
                        Complete

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                                                            Section No.  3-17-
                                                            Date May 31, 1991
                                                            Page 14
o
Table 4.1 (Continued)

Characteristic
Sample logistics
Acceptance limits
Properly label all
bags , containers ,
etc; record all
data on form such
as Fig. 4.2
Frequency and method
of measurement
Visually check each
sample
Action of require-
ments are not met
Complete the
labeling
                                                                                 O
                                                                                 o

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                                                            Section No. 3.17-5
                                                            Date May 31, 1991
                                                            Page 1
5.0   POSTSAMPLING  OPERATIONS
     The  postsampling  operations  include  recovery  of  the  condensible  organic
 fraction contained in the condensate trap, analysis of the carbon  dioxide collected
 during condensible organic  recovery,  and analysis of  the noncondensible organic
 fraction collected during source sampling in the sample tank.   These  operations are
 performed for  the  compliance test  samples,  the  blank  sample  trap/blank sample tank
 set, and the audit samples.
     Both initial  and daily  performance  checks  of  the condensible organic  recovery
 system are  performed.    Initial  performance  checks  include  a  carrier  gas  and
 auxiliary   oxygen  blank  test,  an  oxidation  catalyst  efficiency  check,  and  a
 condensible organic  recovery efficiency  test.  Daily performance checks include a
 recovery  system leak check,  a system background  test,  and  an oxidation  catalyst
 efficiency check.
     Both initial  and daily  performance  checks  and calibration of the NMO  analyzer
 are performed.   Initial performance tests include  an  oxidation catalyst efficiency
 check, a reduction catalyst efficiency check, an analyzer response linearity  check,
 and a  chromatography performance check.   The initial calibration is derived from
 the analyzer linearity  check data.   Daily calibration of both the C02 response and
 NMO  response  is performed.    Figure  5-18 at the  end of  this section provides a
 checklist for monitoring the postsampling operations.  Table  5.1  at  the end  of the
 section  summarizes  the  quality  assurance  activities  associated  with  the
 postsampling operations.

 5.1  Initial Performance Tests

     Initial performance tests of  both the condensible organic recovery system and
 the NMO analyzer are performed before the systems  are first  placed into operation,
 after  any  shutdown of longer  than  six months,  or after any  major modification  of
 the systems.              ...

 5.1.1  NMO Analyzer (see Figure 5.1)

     Oxidation  Catalyst Efficiency  Test - With both catalysts  unheated, perform
 triplicate  analyses  of  the high level methane  standard (nominal 1  percent  CHA  in
 air).   With  the  oxidation   catalyst  heated only to  its operating  temperature,
 reanalyze the  high level methane  standard in  triplicate.   Record data on  a data
 sheet  (Figure  5-2)  and  calculate  the   oxidation  catalyst   efficiency  using the
 equation shown  the figure.  The average response with the oxidation catalyst  heated
 should be less  than 1 percent of the average response obtained with  both  catalysts
 unheated.  If not, replace the oxidation catalyst.

     Reduction  Catalyst Efficiency  Test  - With  the oxidation catalyst unheated and
 the reduction catalyst  heated to its  operating  temperature,  analyze  the high level
 methane  standard  in  triplicate.   Repeat  the  analysis  in  triplicate  with both
 catalysts heated to their  operating  temperatures.   Record  data  on a data sheet
 (Figure 5-2)  and calculate  the reduction catalyst efficiency using the  equation
 shown  the figure.   The  responses observed under these two conditions should agree
 within 5 percent.  If not,  replace the reduction catalyst.

     NMO Response  Linearity  Test and Initial Calibration - With  both catalysts  at
 their  operating temperatures,  perform  triplicate injections of each  of the propane

-------
                                    Section No. 3-17-5
                                    Date May 31, 1991
                                    Page 2
o
                    COLUMN OVEN
                     GC COLUMN
              cgogggggoooooqcqcaxxjciD.
                                        VALVE OVEN
                                              Ho CARRIER
                                                 GAS
OXIDATION
CATALYST
   Figure 5-l«  Nonmethane organic analyzer.
O

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                                                          Section No. 3.17-5
                                                          Date May 31, 1991
                                                          Page 3
 NMO Analyzer Catalyst  Efficiency Testing
 Date
                                  Analyst
Oxidation Catalyst
Temp. , °C
\ '. v.



Reduction Catalyst
Temp., °C




FID Response
Run 1




Run 2



i .
Run 3

;• •


Average

t '
•<•- • , '• .

Oxidation Catalyst Efficiency =
                                Rl -
                                         x 100 (criteria is 99# or greater)
   where:   Rj = Average FID response with both catalysts unheated.
            R2 = Average FID response with oxidation catalyst only heated.
Reduction Catalyst Efficiency =
                                 R,
                                      x 100 (criteria is 95% or greater)
   where:   R3 = Average FID response with reduction catalyst only heated.
            R4 = Average FID response with both catalysts heated.
          Figure 5.2.  Analytical data form for NMO analyzer catalyst efficiency.

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                                                            Section No.  3-17-5
                                                            Date May 31, 1991
                                                            Page 4
o
standards  specified  in Subsection 1.3.5 (i.e., 20  ppm,  200 ppm, and 3tOOO ppm  in
air nominal).   Convert certified  concentrations in  ppm  to  ppm C by multiplying ppm
concentrations  by  3.  Record  these  concentrations  on a data  sheet, such  as  shown
in Figure  5.3,  along with the  area responses observed in each injection.  Calculate
the mean response  factor  as  ppm C/mean area for each standard and the  overall mean
response factor for  all three  standards.   The NMO response linearity is acceptable
if  the average response  factor  of each  calibration gas  standard is within 2.5
percent of the  overall mean  response factor and if the relative standard deviation
for each  set of triplicate  injections  is  less than 2 percent.   If these criteria
are not met,  check the air  and hydrogen flows for the FID to confirm that they are
set according to manufacturer's specifications.   Make adjustments if necessary and
repeat  the test.   The overall mean response  factor is  used as  the  initial NMO
calibration response factor  (RFNMO).

     C02 Response  Linearity Test and  Initial Calibration  -  Perform the linearity
test  as described above,  except use  the  C02  calibration standards  specified  in
Subsection 1.3-5  (50  ppm,   500 ppm,  and   1  percent in  air).   The overall mean
response  factor is  used  as the  initial C02  calibration  response  factor (RFC02).
The C02 calibration  response factor (RFC02) should be within 10 percent of the NMO
calibration factor (RFNMO).  If not, repeat the oxidation  catalyst  efficiency  test.

     NMO  Analyzer  Performance Test -  After  calibration  of  the  NMO  response  as
described  above, analyze each of  the test  gas  mixtures  specified in Subsecti/  "\
1.3.5 in  triplicate.   (Standard  1  is nominally  50 ppm CO, 50  ppm CHA ,  2 percertv_X
C02, and 20 ppm propane in  air; Standard 2 is 50 ppm hexane in air; Standard 3 is
nominally  20  ppm  toluene in  air;   and  Standard  4  is 100  ppm methanol  in   air.)
Record the NMO  area  responses  for  each  test  gas  on  a data sheet such as shown in
Figure 5.4.   Convert the  certified  organic compound concentrations of the test gas
mixtures  to ppm C  by multiplying  by  the carbon  number of  the  compound  (3 for
propane, 6 for hexane,  and 7 f°r toluene).   Record  these concentrations on the data
sheet as the  expected  concentrations.   Calculate  the mean NMO concentration of the
test gas  using  the  equation  shown in Figure 5.4.   The  analyzer performance  is
acceptable if the  average measured NMO concentration for  each mixture  is within 5
percent of the expected value.

5.1.2  Condensible Organic "Recovery System

     Carrier  Gas and Auxiliary Oxygen  Blank Check  - Each new  tank of zero  grade
air and zero grade  oxygen  is analyzed  with  the  NMO  analyzer according  to the
procedure  described  in  Subsection  5.4.2.    The  total   concentration   from any
measured methane, carbon monoxide, carbon dioxide, or nonmethane organics should be
less than  5 parts-per-million  carbon (ppm  C).  Record data on a data sheet such as
shown in Figure 5•5•

     Oxidation  Catalyst Efficiency  Test - Perform  this  test using the equipment
shown in Figure 5-6  and the  following procedure:
       1.   Install a clean sample trap in the recovery system.
       2.   Replace  the zero  air  carrier  gas with the  high  level   methane S8?-*\
           standard  (1 percent  methane in air nominal concentration).            (    )
       3.   Set  the  4-port  valve  to the   trap recovery  position  and  the  sampTb	/
           recovery valve to the vent position.   Establish a 100 cm3/minute flow of
           the methane in air  standard.
       4.   Attach an intermediate collection vessel  (ICV)  to the recovery system.

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                                                            Section No. 3.17-5
                                                            Date May 31, 1991
                                                            Page 5
                           NMO Analyzer Linearity Testing
Date
                           Analyst
Compound
Propane
Propane
Propane
C02
C02
C02
Cone . ,
ppm C






FID Area Response
Run 1






Run 2






Run 3






Mean






RSD






HP.
ppm C/Area






Overall
Mean RF






Percent
Difference






                              RF - Overall Mean RF
       Percent Difference
                                      x 100
                              Overall Mean RF
       RSD =
 100
 ••••—•••I

  R
                          n - 1
where:   R
        Ri
         n
Mean RID response.
FID response for run i,
Number of runs.
           Mean RF =
                      Standard Cone, (ppm C)
                      Mean Area Response (R)
         Overall Mean RF  =
         (RFNMO or RFC02)
                                    RF2 + RF3
        Figure 5.3.   Analytical data form for NMO analyzer linearity tests.

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                                                          Section No.  3.17-5
                                                          Date May 31,  1991
                                                          Page 6
                         NMO Analyzer Performance Testing
                                                                            o
Date
                                 Analyst
Test Gas
Propane Mix
Hexane
Toluene
Methanol
NMO Area Response
Run 1




Run 2

--•*


Run 3




Mean




RFNMO •
ppm C/Area




Mean Cone . ,
ppm C




Expected
Cone. , ppm C




Percent
Diff.




     Mean Cone. = Mean NMO Area x RF,
                                    NMO
     Percent Difference = Mean Cone. - Expected Cone.
                                Expected Cone.
                                                                                   O
Figure
                    Analytical data form for NMO analyzer performance test.
                                                                                    O

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                                                          Section No. 3-17-5
                                                          Date May 31, 1991
                                                          Page 7
                      Analysis  of Recovery  System Carrier Gases
 Date
            Analyst
 Cylinder  No.
                  Peak Area
CO  C02  NMO
                                     RF
                                     fir,
                                       NMO
                            Concentration, ppm C
CH4  CO  C02  NMO
   Concentration, ppm C = RFNMO x Peak Area
Total,
ppm C
Figure 5.5-  Analytical data form for analysis of recovery system carrier gases.

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                                                           Section No.  3-17-5
                                                           Date May 31, 1991
                                                           Page 8
                                                                       o
                    FLOW METERS
                            \
                                                 HEAT TRACE (100'C).
                                          SAMPLE
                                         RECOVERY
                                           VALVE
                         FLOW
                        CONTROL
                         VALVE
                                                     SYRINGE PORT
                                                                                     O
       VACUUM PUMP
Figure 5.6.
Condensible organic recovery system oxidation catalyst efficiency  test.O

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       7.
       8.
                                                 Section No.  3.17-5
                                                 Date May 31,  1991
                                                 Page 9

With the  flow  control  and ICV valves fully open, open  the vacuum valve
to evacuate the manometer or gauge,  connecting tubing, and the ICV to 10
mm  Hg  absolute  pressure or  less.    Close  the  vacuum  valve and  flow
control valve.
Once the  NDIR  analyzer response  is  stable,  switch  the  sample recovery
valve to  the  collect position.   When  the manometer or  gauge  begins to
indicate  pressure  above  atmospheric,  open  the  flow  control valve  to
maintain  atmospheric pressure in the  system.   After fully  opening the
flow control valve,  continue  pressurizing the ICV  to a nominal gauge
pressure of 300 mm Hg (1060 mm Hg absolute).
Switch the sample recovery valve back to the vent position.
Close the ICV  valve and  detach the ICV  from  the system.   Replace the
methane standard with the zero air carrier gas.
Analyze the C02  concentration in the  ICV using  the NMO  analyzer.   The
C02 concentration  should be  within  2 percent of the  methane standard
concentration.   Record data on a  from  such as  that  shown in Figure  5*7-
If the test criteria cannot be met, repack  the  oxidation catalyst  tube
with new material as described in Subsection 1.2.1.
     Condenstble Organic  Recovery Efficiency Test  -  This test  is  performed
the equipment shown in Figure 5«8 and the following recommended procedure:
                                                                   using
                    the
                    the
             liquid sample  injection unit  in
             end with  the tee  to  the tubing
place  of a  sample
terminated at  the
trap.
-port
                                                                         to  nominal
                                                                             sample
      5-
      6.
      8.
     10.
     11
     12
is 100 i
each set
recovery
      Install
      Connect
      valve.
      Set  the zero  air carrier  gas  and  auxiliary  oxygen  flows
      levels of 100 cm3/minute and 150 cm3/minute, respectively.
      Set  the 4-port  valve  to the  trap  recovery  position  and  the
      recovery valve to the vent position.
      Attach  an  intermediate  collection  vessel  to   the  recovery  system.
      Evacuate the ICV, manometer or  gauge,  and connecting tubing to 10 mm Hg
      absolute pressure or less.  Close the vacuum and flow control valves.
      Switch the sample recovery valve to the collect position.
      Inject  50  microliters  of hexane  into the  septum  port of  the  liquid
      sample injection unit.
      Continue recovery  of the  injected organic  as described  in Subsection
      5.3-2.
      Record  the  final ICV volume  and ICV pressure on  a form  such  as  that
      shown in Figure 5-9 and detach the ICV from the recovery system.
      Determine the  C02  concentration of  the  ICV by analysis using  the NMO
      analyzer and record on a form such as that in Figure 5-9.
      Calculate the percent recovery using the equation on a form such as that
      shown in Figure 5.9.
      Repeat  the  recovery  test  two  additional  times  with 50  ul  hexane
      injections.
      Perform additional recovery tests in triplicate with 10 ul hexane, 50 ul
      decane, and 10 ul decane each.
The recovery system performance is  acceptable if the average percent recovery
    10  percent with a relative standard deviation of less than 5 percent for
     of triplicate  analyses.    If  these requirements are not met,  check the
     system  for   leaks  and  ensure  adequate  heating  of the liquid  sample
injection unit during recovery.

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                                                          Section No. 3.17.5
                                                          Date May 31, 1991
                                                          Page 10
                     Recovery System Oxidation Catalyst  Testing
                                                         o
     Date
          Analyst

C02 Area Response
of ICV
i.
RFC02
ppm/area

C02 Cone . ,
ppm

Cfy Std.
Cone. , ppm

Percent
Difference

                                                                                  O
    Percent Difference
°°?
                                         Std> C°nC> X 10°
                              CHj| Std. Cone.

    C02 Cone. = C02 Area Response x RFC02
Figure 5.7.  Analytical data form for recovery system oxidation catalyst testing.
                                                                                   O

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                                                 Section No. 3.17-5
                                                 Date May 31, 1991
                                                 Page 11
            FLOW METERS
                    \
                                       HEAT TRACE (100°C)
                     AIR
                            LIQUID
                            SAMPLE
                            INJECTION
                            IMF—-OCtl
                                SAMPLE
                               RECOVERY
                                 VALVE
                FLOW
               CONTROL
                VALVE
SYRINGE PORT
 CJ
VACUUM PUMP
                       ICV
                            CV
                           VALVE
      Figure 5»8.   Condensible organic recovery efficiency test.

-------
                                     Condensible Organic Recovery Efficiency Testing
          Date
                    Analyst
Compound
Hexane
Hexane
Hexane
Hexane
Hexane
Hexane
Decane
Decane
Decane
Decane
Decane
Decane
Molecular
Weight,
g/g-mole
86.18
86.18
86.18
86.18
86.18
86.18
142.29
142.29
142.29
142.29
142.29
142.29
Density,
g/ml
0.661
0.661
0.661
0.661
0.661
0.661
0.730
0.730
0.730
0.730
0.730
0.730
Volume
Injected,
uL
10
10
10
50
50
50
10
10
10
50
50
50
Collection Tank Data
Volume, Temp., Pressure,
m3 °K mm Hg












C02 Cone. ,
pprn












% Recovery



'•-








Overall Mean,
% Recovery












RSD
Percent












 Percent Recovery  =  1.604
	(Molecular Weight)(Tank Volume)(Tank Pressure)(CO, Cone.)	

(Volume Injected)(Liquid  Density)(Tank Temp.)(Carbon Number of Compound Injected)
                   100
          RSD  =
                                 n - 1
where: J!R1 = Percent  recovery for an individual test.
       %Ri = Overall  mean percent recovery for a compound and injection volume.
         n = Number of tests (3).
                          Figure 5.9.  Analytical data form for recovery efficiency test.

      O                                                O
                                                                                       13 O Cfl
                                                                                       ffl P fi>
                                                                                       W rr O
                                                                                       (D 0> cr

                                                                                       ^ 3 O
                                                                                       W» 3

                                                                                           "Z,
                                                                                         UO O
                                                                                           00
                                                                                         !-' •
                                                                                         V£> H»
                                                                                         VD-4
                                                                                         l-» •
                                                                                           VJl
                                                                                    O

-------
                                                            Section No.  3-17.5
                                                            Date May 31,  1991
                                                            Page 13
 5.2  Daily Performance Tests
 5.2.1  Condensible Organic "Recovery System {see Figure 5-10) - Complete three tests
 each day before recovery of any samples.

     Leak Test - Completely close the zero air and auxiliary oxygen metering valves
 and the  flow control valve.   Install a clean sample  trap  in  the system and switch
 the  sample  recovery  valve  to  the  collect position.   Open  the vacuum valve  and
 evacuate the system  to  10 mm  Hg absolute  pressure or less.  Close the vacuum valve
 and  record  the initial pressure on  a data  sheet such as  shown in  Figure 5.H-
 After  10 minutes,  record the  system pressure.  The pressure  change  should be less
 than 2 mm  Hg over the  10-minute period.  If  not,  locate leakage by an appropriate
 method such as pressurizing  and checking fittings with water.   Repair  leaks  and
 retest as described above.

     System  Background  Test  -  Set  the carrier gas  and auxiliary oxygen  flows to
 their  normal values of  100 cm3/minute and 150 cm3/minute,  respectively.  Switch the
 4-port valve to the  trap  recovery  position  and  the  sample recovery  valve to  the
 vent position.   Use  a  10  cm3 syringe to withdraw a sample from  the syringe port
 located upstream  of  the NDIR analyzer.  Flush the  gas sampling loop on the  NMO
 analyzer with the syringe  sample and  then switch the sampling valve  to inject.
 Record the C02 peak area on a data sheet such as shown in Figure 5-12 and calculate
 the  C02  concentration.    The  system  background  is   acceptable  if  the  C02
 concentration measured  is  less  than  10 ppm.   If the  background  concentration is
 greater than 10 ppm,  purge  the recovery system with  carrier  gas and heat the trap
 connecting tubing to remove residual organics, then repeat the background test.

     Oxidation  Catalyst Efficiency  Test  -  Conduct  this  test as  described  in
 Subsection  5-1•!•    If  the  test criteria  cannot  be  met,  replace  the  oxidation
 catalyst and retest.

 5.2.2  NMO Analyzer Daily Calibration

     C02  Response  Calibration  -  Analyze the highest  level  (\%) C02  calibration
standard three times.  Record the C02  peak areas on a data sheet such as that shown
 in Figure  5.13 and  calculate  the  average  daily response  factor  (DRFC02).   The
average daily response  factor (DRFC02) should  be within  5 percent  of the initial
C02 calibration response factor (RFC02).    If not, repeat  the  initial performance
 test as described in Subsection 5.1.2 to establish a new RFC02.   The daily response
 factor is used to quantitate the C02 concentrations of the ICV samples.

     NMO  Response  Calibration -  Analyze   the   gas  mixture   containing  nominal
concentrations of 50  ppm CO,  50 ppm CHA,  2 percent C02, and  20  ppm  propane in air
in triplicate.  Record the NMO  peak  areas  on  a  data sheet such as  that  shown in
Figure 5'13  and calculate the average daily  response  factor (DRFNMO).  The average
daily  NMO response  factor  (DRFNMO)  should be within  5 percent  of  the initial  NMO
response factor (RFNMO).  If  not, repeat  the  initial  performance test as described
 in Subsection 5«1«2 to establish a new RFNMO.  The daily response factor is used to
quantitate the NMO concentration of the sample tanks.

-------
                                                   Section No. 3.17.5
                                                   Date May 31, 1991
                                                   Page 14
                  o
             FLOW METERS
                                          HEAT TRACE (100°C).
                                   SAMPLE
                                  RECOVERY
                                   VALVE
                 aow
                CONTROL
                 VALVE
SYRINGE PORT
                                                                             O
VACUl/M PUMP
                 Figure 5.10.  Condensate  recovery system.
                  O

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                                                            Section No.  3.17-5
                                                            Date May 31,  1991
                                                            Page 15
                      Condensate Recovery System Leak Testing
Date
Analyst
Initial
 Time
Initial Press.,
     Torr
Final Time
Final Press.,
  Torr
         Figure  5.11.   Analytical  data form for recovery system leak test.

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                                                            Section No. 3.17-5
                                                            Date May 31, 1991
                                                            Page 16
                    Condensate Recovery System Background Testing
Date
Analyst
  RFC02 •
ppm/Area
C02 Peak Area
CO, Cone.,  ppm
                                                                            o
                                                                                     o
     C02 cone.,  ppm = CO- Peak Area x RF,
                                        C02
       Figure 5.12.  Analytical data form for recovery system background test.
                                                                            O

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                                                           Section No. 3.17.5
                                                           Date Hay 31, 1991
                                                           Page 17
                           Daily NMO Analyzer Calibration
Date
Analyst
NMO Calibration Cylinder No.
             CO,  Calibration Cylinder No.
Compound

Cone . ,
ppm C

FID Area Response
Run 1

Run 2

Run 3

Mean

DRF,
ppm C/Area

Initial
RF

Percent
Diff.

     Percent Difference = DRF " Initial RFx 100
                            Initial RF
                                R
     Mean Area Response =
     where:  RA  =  FID area response.

               Concentration
     DRF  =
          Mean Area Concentration
     Figure 5-13.  Analytical data  form for daily calibration of NMO analyzer.

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                                                            Section No.  3-17.5
                                                            Date May 31.  1991
                                                            Page 18
5.3  Condensible Organic Fraction Recovery
o
     Recovery of  condensible organics is  accomplished in  two  steps.    First,  the
condensate trap  is purged  of carbon dioxide  while cooling  the  trap  in  dry  ice.
Second,  the  condensible organics  are volatilized  and converted  catalytically  to
carbon dioxide which  is collected in an intermediate collection  vessel (ICV)  for
analysis.

5.3.1  Trap Purge  and Sample Tank  Pressurizatton  -  The following procedure is used
to purge carbon dioxide from the condensate  trap  and to pressurize the sample tank
(see Figure 5.1*0:
   1. Obtain the  sample tank and  condensate trap from  the source test run  to  be
      analyzed (or the blank' sample tank and blank condenste trap).
   2. Set  the  zero  air carrier  gas to a  flow  rate  of  100  cm3/minute  and  the
      auxiliary oxygen flow  to zero.
   3. Switch the *J-port valve to the C02 purge position.
   4. Attach the sample tank to the condensate trap recovery system.
   5. With the  sample  recovery  valve in  the vent  position  and  the  flow control
      valve fully open, evacuate the manometer or gauge to the expected pressure of
      the sample tank.
   6. Close the  vacuum valve, open  the sample tank valve, and  record  the sample
      tank pressure  (Pt) in mm Hg absolute  on a  data sheet such  as that  shown in
      Figure 5.15.
   7. Immerse the  condensate trap in crushed dry  ice and attach  to  the  recovery^—^
      system with  the  trap outlet  connected to the  tube  terminating at  the k-port(   j
      valve.                                                                        V	/
   8. Switch the  sample recovery  valve  from vent  to collect.   Adjust  the  flow
      control valve to  maintain approximately atmospheric pressure in  the recovery
      system.
   9. After the  NDIR analyzer responds  to  the C02 purged  from  the  trap and  the
      response reaches  a minimum  level,  withdraw  a  10  cm3  syringe sample  from the
      syringe port and analyze with  the NMO analyzer.  Repeat analyses until  the
      C02 concentration of the trap  effluent is  less  than 5 ppm.  The length of
      time required to purge the trap of residual  C02 will depend upon the internal
      volumes of the condensate trap  recovery system.   A larger volume system will
      require more purging time  at the  specified flow rates to  meet  the  effluent
      concentration criteria of less than 5 ppm.
  10. Switch  the  carrier   gas  bypass   valve  to   pressurize  the  sample   tank  to
      approximately 1060 mm Hg absolute pressure.   Switch the sample recovery valve
      to the vent  position and record the final  sample  tank  pressure  (Ptf) on the
      data sheet.  Detach the sample tank from the system.

5-3'2  "Recovery of Condensible Organics -  The following procedure is used to purge
organics from  the sample  trap,  convert  them to  carbon  dioxide,  and collect  the
carbon dioxide in an intermediate collection vessel  (see Figure 5.16).
   1. Attach an  ICV to the  trap  recovery system.   Open the flow control and ICV
      values fully and evacuate the manometer or gauge, connecting tube,  and ICV to
      10 mm  Hg  absolute  pressure  or less.   Close the  flow  control  and vacuum
      valves.
   2. Set the auxiliary oxygen flow to a rate of 150 cm3/minute.                    /"""N
   3. Switch  the  4-port   valve  to  the  trap  recovery  position  and  the  sample (   J
      recovery  valve  to  the  collect position.    After  the  system  reaches ^—
      atmospheric  pressure,  adjust the  flow  control valve to maintain  atmospheric
      pressure within 10 percent.

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                                                  Section No.  3.17.5
                                                  Date May  31,  1991
                                                  Page 19
             FLOW METERS
                     \
                                          HEAT TRACE (100°C)
                                   SAMPLE
                                  RECOVERY
                                    VALVE
                  FLOW
                CONTROL
                 VALVE
                                     SYRINGE PORT
VACUUM PUMP
SAMPLE
 TANK
               Figure 5.14.  Condensate recovery system,  CO  purge.

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                                                            Section No. 3.17-5
                                                            Date May 31, 1991
                                                            Page 20
Date 	
Location
Run No.
               Analyst
	  Plant _
 Date Sampled
                                                                                    o
                             Trap No.
Sample Tank No.
                                                ICV No.
ICV volume, m3 (Vv)
Sample tank pressure after sampling, mm Hg (Pt)
Sample tank pressure after pressurizing, mm Hg {Ptf)
ICV final pressure, mm Hg (Pf)
ICV volume, m3 (Vv)
Sample tank temperature after pressurizing, °K (Ttf)
ICV final temperature, °K (Tf)   ,
Sample tank temperature at end of sampling, °K (tt)
Sample tank temperature before sampling, °K (Tti)
Sample tank pressure before sampling, mm Hg (Ptl)
Gas volume sampled, dsm3 (Vg)
Run
No.
1
2
3
Mean
ICV Analysis
C02 Area


C02 Cone . ,
PPm (Ccnl)


NMO Area


NMO Cone . ,
ppm C (Ccm2)

,
Sample Tank Analysis
NMO Area


NMO Cone . ,
PPm c (ctm)


                                                                                    o
   C02 Cone. = C02 Area x
   NMO Cone. = NMO Area x DRFMMn
                             ri jn u
                                  rtf

                                  T
                                  Atf
Noncondensible Organic    =   -=	=—
Concentration, ppm C (Ct)      _J_	t^
                                     IT—x ct»
                                     V  P
                                     vv rf
                                              x  <% + Ccm2 )
Condensible Organic       = 0.3857
Concentration, ppm C (Cc)

TGNMO Concentration, ppm C = Ct - Ctb + Cp - Ccb*

*Note: Blank subtraction must have prior approval of the Administrator.


        Figure 5-15-  Analytical data form for sample recovery and analysis.
                                                                                    O

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                                                   Section No. 3.17-5
                                                   Date May 31, 1991
                                                   Page 21
             FLOW METERS
                                          HEAT TRACE (100°C).
                                   SAMPLE
                                  RECOVERY
                                   VALVE
                 FLOW
                CONTROL
                 VALVE
SYRINGE PORT
VACUUM PUMP
   Figure 5*16.  Condensate recovery  system,  collection of trap organics,

-------
o
                                                            Section No.  3-17.5
                                                            Date May 31, 1991
                                                            Page 22

   4. Remove the condensate trap from the dry  ice  and  allow ambient air warming of
      the trap while  monitoring the NDIR analyzer response.   The auxiliary oxygen
      flow may  be discontinued  after five  minutes  if the  C02  response  is below
      10,000 ppm (1%).
   5. Heat the  trap by placing  it in a  furnace at 200° C.   If  the  NDIR response
      exceeds 50,000  ppm  (5#) during recovery,  resume auxiliary oxygen  flow at a
      rate of 150 cm3/minute.
   6. After  the  NDIR analyzer  indicates  a C02  concentration  of less  than 10,000
      ppm,  begin  heating  the  tubing  connecting  the  condensate  trap  to  the
      oxidation catalyst with a heat gun.  Heat  the  tubing  slowly along the entire
      length from the trap 'to tfhe catalyst,  and repeat two additional times.
   7. Continue trap  heating and purging  until the  C02  concentration  is  below 10
      ppm (determined by  analyzing syringe samples  collected  before  NDIR analyzer
      with the NMO analyzer).
   8. When recovery  is  complete,  switch the  carrier gas bypass  to pressurize the
      ICV to approximately  1060 mm Hg.   Switch  the sample  recovery  valve to vent
      and record the ICV final pressure  (Pf)  on  a  data sheet such as that shown in
      Figure 5-15.

5-4  Analysis

     The total source concentration of gaseous nonmethane organics is determined by
combining the  noncondensible and  condensible concentrations.    The noncondensible
concentration is determined by  analyzing the sample tank for  nonmethane organics,
and  the condensible  concentration  is  determined by  analyzing the  intermediate
collection vessel for C02.

5.4.1  NMO Analyser Operating Conditions  - Set the helium carrier gas flow rate to
30 cm3/minute.   Set  the  oxidation  catalyst oxygen flow  rate to  2.2  cm3/minute.
Heat the column oven to an initial temperature of 85°C.

5.^.2   Intermediate  Collection Vessel  Analysts  - Analyze the  ICV  contents as
follows:
   1. Attach the ICV to the 10-port gas sampling valve.
   2. Purge the sample loop with gas from the ICV and then switch the 10-port valve
      to the inject position.
   3. When the detector response  returns to near  baseline  following the C02 peak,
      switch the  10-port  valve to  the backflush position and  increase the column
      oven temperature to 195°C as rapidly as possible.
   4. After detection of  any nonmethane  organic compounds,  return  the  column oven
      temperature to 85°C.
   5. Record the C02 peak area  and NMO peak  area on the data sheet shown in Figure
      5.15-
   6. Repeat the analysis two additional times.
   7. Calculate C02 and NMO concentrations using equations given in Figure 5.15.
   8. Calculate   the  average  C02  concentration  (Cc(nl)   and  the  average  NMO
      concentration (Ccin2) in the ICV and record on the data sheet.

5.4.3   Sample Tank  Analysis -  Analyze  the  sample tank  as described  in Section
5.4.2.  Record the  NMO  peak area only and calculate the  average NMO concentration  f-^.
(Ctra) of the sample tank.                                                             f   j
 o

-------
                                                            Section No. 3-17-5
                                                            Date May 31. 1991
                                                            Page 23

5.4.4  Condensible Organic Blank Analysis -
      1.  Analyze the  ICV resulting from  the  blank trap recovery  as  described in
          Section 5.4.2.
      2.  Calculate  C02  and  NMO concentrations  using equations  given in  Figure
          5.16.
      3.  Calculate  the  average C02  concentration  (Ccnl)  and  the   average  NMO
          concentration (Ccm2) in the blank ICV and record on the data sheet.
      4.  Calculate  the source condensible organic  blank concentration (Ccb) using
          the equation in Figure 5-17-  The condensible organic blank concentration
          may not exceed  15 ppmC.   If the blank value exceeds 15 ppmC,  then the
          value of 15  ppmC  may be used as the blank value.   NOTE:  The method does
          not provide  for blank correction.   However,  with prior  approval  of the
          Administrator,  blank  correction (subtracting  the blank  value)  may be
          used.

5-4.5   Noncondensible Organic Blank Analysis - Analyze  the blank sample tank as
described  in Section  5-4.2.    Record the NMO peak  area  only and calculate the
average NMO  concentration  (Ctmb)of  the  blank sample  tank.   Calculate the source
noncondensible  organic blank concentration   (Ctb)  using  the  equation  shown in
Figure  5-17-    The   noncondensible  organic blank  concentration may  not  exceed 5
ppmC.  If the blank  value exceeds 5  ppmC,  then the  value of 5 PpmC may be used  as
the  blank value.    NOTE:  The  method  does  not  provide   for blank correction.
However, with  prior  approval of the Administrator, blank  correction   (subtracting
the blank value) may be used.

5.4.6   Source  Concentration  Calculations -  Calculate the  noncondensible organic
concentration  (Ct),  the  condensible  organic concentration (Cc),  and the TGNMO
concentration using  the  data and  equations  shown Figures  5.15  and  5.17  (blank
subtraction requires  prior approval of Adminstrator).

-------
                                                            Section No. 3-17-5
                                                            Date Hay 31, 1991
                                                            Page 24
Date 	
Location 	
Blank No. 	
Sample Tank No.
               Analyst
	  Plant _
 Date Sampled
                                                                                    o
                                 Trap No.
                                                ICV No.
ICV volume, o3 (Vv)
Sample tank pressure after sampling, nun Hg (Pt)
Sample tank pressure after pressurizing, mm Hg (Pt t)
ICV final pressure, mm Hg (Pf)
ICV volume, ra3 (Vv)
Sample tank temperature after'ipressurizing, °K (Ttf)
ICV final temperature, °K (Tfj
Sample tank temperature at end of sampling, °K (Tt)
Sample tank temperature before sampling, °K (Ttl)
Sample tank pressure before sampling, mm Hg (Ptl)
Gas volume sampled, dsm3 (VB)
Blank
No.
1
2
3
Mean
ICV Analysis
C02 Area


C02 Cone . ,
PPm (Ccml)


NMO Area


NMO Cone . ,
PPm c 
-------
                                                            Section No.  3.17-5
                                                            Date May 31, 1991
                                                            Page 25
 Date         Plant Name 	 Sampling Location
 Initial Performance Tests of Condensible Organic Recovery System

 Do  zero grade air and zero grade oxygen carrier gases contain less than 5 Ppm C
    total of methane, carbon monoxide, carbon dioxide, and nonmethane organics?
    	 yes  	 no.  (If no, replace gases or filter to remove impurities.)
 Does the C02 concentration in the ICV collected during the oxidation catalyst
    efficiency test agree within 2 percent of the methane standard concentration?
    	 yes  	 no.  (If no, replace the oxidation catalyst.)
 Is  recovery efficiency  100  +_ 10 percent with a relative standard deviation of less
    than 5 percent for each set of triplicate injections of hexane and decane at
    10 ul  and 50 ul?   	 yes   	 no.   (If  no,  check the  recovery system for
    leaks and assure adequate heating of the liquid sample injection unit.)

 Initial Performance Tests of NMO Analyzer

 Does the oxidation catalyst efficiency test show an efficiency of 99 percent or
    better?  	 yes  	 no.  (If no, replace the oxidation catalyst.)
 Does the reduction catalyst efficiency test show an efficiency of 95 percent or
    better? 	 yes  	 no.   (If no, replace the reduction catalyst.)
 Is  the NMO response linear?  (Average response factor of each calibration standard
    within 2.5 percent of the overall mean and a relative standard deviation for
    each set of triplicate injections of less than 2 percent.)  	 yes  	 no.
  (If no, check FID air and hydrogen flows and make adjustments.)
 Is  the C02 response linear?   (Average response factor of each calibration standard
   within 2.5  percent  of the  overall mean  and  a relative standard  deviation for
   each set of triplicate injections of less than 2 percent).   	  yes  	 no.
    (If no, check FID air and hydrogen flows and make adjustments.)
Are the measured concentrations of the analyzer performance test gases within 5
   percent of their certified  concentrations?  	 yes  	 no.   (If no, replace
    the GC  column or adjust  column backflush  timing and/or temperature  to obtain
   acceptable performance.)

Daily Performance Tests of Condensible Organic Recovery System

Leak test completed? 	 yes  	no.  (Leak test following procedure in Sub-
   section 5.2.1.)
System background test completed? 	 yes  	 no.   (Follow procedure in Sub-
   section 5.2.1.)
Oxidation catalyst efficiency test completed? 	 yes  	 no.  (Follow procedure
   in Subsection 5.2.1.)

Daily Calibration of NMO Analyzer

Calibration of C02 response completed with 1% C02 in air standard?
   	 yes  	 no.
Calibration of NMO response completed with mixed gas standard containing 50 ppm
   CO,  50 ppm CH4, 2 percent C02, and 20 ppm propane in air? 	 yes  	 no.

                 Figure 5.18.   Postsampling  operations  checklist.

 (Continued)

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                                                            Section No. 3.17-5
                                                            Date Hay 31, 1991
                                                            Page 26

Figure 5.18. (Continued)

Condensible Organic Recovery

Condensate trap purged and sample tank pressurized? 	 yes  	 no.  (Follow
   procedure in Subsection 5 • 3 • 1 •)
Condensible organics purged from sample trap, converted to C02, and collected in
   an ICV? 	 yes  	 no.  (Follow procedure in Subsection 5-3-2.)

Analysis of Sample Tank and Intermediate Collection Vessel
                        j .  .,^ .  ;

NMO analyzer operating conditions set? 	 yes  	 no.  See Subsection,5-4.1..)
ICV analyzed in triplicate? 	 yes  	 no.  (Follow procedure in Subsection
   5.4.2.)
Sample tank analyzed in triplicate?	 yes  	 no.  (Follow procedure in
   Subsection 5.4.3.)
Source concentration calculated? 	 yes  	 no.  (Use equations shown in
   Figure 5.1.5.)
                                                                                   o
                                                                                    o

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                                                            Section No.  3.17.5
                                                            Date May 31,  1991
                                                            Page 27
                  Table 5.1.    ACTIVITY MATRIX FOR SAMPLE ANALYSIS
 Characteristic
Carrier gas and
auxiliary 02 used
in condensible
organic recovery
system
Recovery system
oxidation catalyst
efficiency
    Acceptance
      limits
Total concentration
from CH4, CO, C02,
and NMO must be
<5 ppm C
C02 concentration
of collected sample
must be +. 2% of CHA
test gas concentra-
tion
Frequency and method
   of measurement
Analyze each new
cylinder with the NMO
analyzer
Before first operation
after any shutdown of
longer than 6 months,
after modification, or
daily when samples are
analyzed; test by re-
placing carrier gas
with 1% din in air,
collection of sample
in ICV, and analysis
with NMO analyzer
 Action if
 requirements
 are not met
 Obtain better
 grades of gas
 from vendor or
 filter gases to
 reduce impurities
Replace oxida-
 tion catalyst
Condensible organ-
ic recovery
efficiency
Average recovery of
100 + 102 with a RSD
of <5# for each set
of triplicate analy-
ses
Before first operation
after any shutdown of
longer than 6 months,
or after modification;
test with 10 and 50 ul
injections of hexane
and decane into liquid
sample injection unit
and analysis of col-
lected sample with
NMO analyzer
 Check recovery
 system for leaks
 and assure
 adequate heating
 of liquid sample
 injection unit
 during recovery
NMO analyzer oxi-
dation catalyst
efficiency
FID response with
oxidation catalyst
heated must be <1%
of response with
both catalysts un-
heated
Before first operation
after any shutdown of
longer than 6 months,
or after modification;
analyze 1% CHA in air
with both catalysts
unheated and then with
oxidation catalyst
only heated
 Replace
 oxidation
 catalyst
(Continued)

-------
Table 5.1 (Continued)
                                                            Section No. 3.17.5
                                                            Date May 31. 1991
                                                            Page 28
                                                               o
 Characteristic
    Acceptance
      Limits
Frequency and method
   of measurement
Action if
requirements
are not met
NMO analyzer
reduction
catalyst
efficiency
Analyzer response
to 1% methane in air
standard with both
catalysts heated
should agree +_ 5% of
response, with re-
duction catalyst
only heated
Before first operation
after any shutdown of
more than 6 months, or
after modification; a
1% CH4 in air standard
is analyzed with both
catalysts heated and
with the reduction
catalyst only heated
Replace
reduction
catalyst
NMO response lin-
earity and cali-
bration
Response factor of
each calibration
gas standard must be
+2.5% of overall
mean response factor
and relative stan-
dard deviation of
each set of trip-
licate analyses
must be <2%
Before first operation
after any shutdown of
longer than 6 months,
or after modification;
analyze propane in air
standards with NMO
analyzer under normal
operating conditions
Check air and
hydrogen flows
for FID to con-
firm that they
are set accord-
ing to manufac-
turer's speci-
fications ; make
adjustments if
necessary and
and repeat test
                                                                                    O
C02 response
linearity and
calibration
Response, factor of
each calibration
gas standard must
be +2.5% of overall
mean response factor
and relative stan-
dard deviation of
each set of tripli-
cate analyses must
be < 2%
Before first operation
after any shutdown of
longer than 6 months,
or after modification;
analyze the C02 stan-
dards with NMO analy-
zer under normal oper-
ating conditions
Check air and
hydrogen flows
for FID to con-
firm they are
set according
to manufacturer's
specifications;
make adjustments
if necessary and
repeat test
NMO analyzer
performance
Average concentra-
tion based on trip-
licate analysis
must be within 5%
of expected value
for each test
mixture
Before first operation
after any shutdown of
longer than 6 months,
or after modification;
analyze test mixtures
with NMO anlayzer
under normal operating
conditions
Replace GC
column or
adjust column
backflush timing
and/or tempera-
ture to obtain
acceptable
performance
(continued)
                                                                O

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 TABLE 5.1   (continued)
                                                            Section No. 3-17-5
                                                            Date May 31, 1991
                                                            Page 29
  Characteristic
 Condensible
 organic recovery
 system leak test
Recovery system
background test
    Acceptance
      Limits
System should lose
<2 mm Hg vacuum
over a 10-min period
The measured C02
background concen-
tration must be <10
ppm
Frequency and method
   of measurement
Daily, before analysis
of samples; evacuate
the recovery system
and monitor the vacuum
with mercury manometer
or pressure gauge
Daily, before analysis
of samples; analyze
syringe samples of
.recovery system efflu-
ent with NMO analyzer
Action if
requirements
are not met
Locate leakage
by appropriate
method such as
pressurizing
and checking
fittings with
water; repair
leaks and retest
Purge recovery
system with
carrier gas and
heat trap con-
necting tubing
to remove res-
idual organics,
then retest
C02 response
calibration
The average response
factor from tripli-
cate analysis of
highest concentra-
tion standard must
be +$% of initial
C02 response factor
Before and after anal-
ysis of each set of
samples or daily,
whichever occurs
first, analyze high-
est level C02 standard
with NMO analyzer
under normal operating
conditions
Repeat analyzer
catalyst effic-
iency tests,
linearity tests,
and performance
test
NMO response
calibration
Average NMO response
factor should be +
of initial NMO
response factor
Before and  after  anal
ysis of each set  of
samples or  daily,
whichever occurs
first, analyze gas
mixture containing
50 ppm CO,  50 ppm CH4,
2% C02, and 20 ppm
propane in  air
Repeat analyzer
catalyst effic-
iency tests,
linearity tests,
and performance
test
Sample trap
purge and
sample tank
pressurization
(Continued)
C02 concentration of
syringe port samples
must be less than
5
Analyze syringe port
samples with NMO
analyzer after NDIR
analyzer response
returns to baseline
Continue purg-
ing trap with
carrier gas and
analyze addi-
tional syringe
port samples

-------
                                                            Section No.  3.17.5
                                                            Date May 31. 1991
                                                            Page 30
TABLE 5.1 (continued)
                                                              o
 Characteris tic
    Acceptance
      Limits
Frequency and method
   of measurement
Action if
requirements
are not met
Condensible
organics recovery
C02 concentration of
syringe port samples
must be <10 ppm
Analyze syringe port
samples with NMO anal-
yzer when NDIR anal-
yzer response returns
to baseline
Continue heating
of sample trap
and purging with
carrier gas
Intermediate
collection vessel
analysis
Relative standard
deviation from trip-
licate analysis for
C0  and NMO must be
Analyze ICV after trap
recovery by injecting
aliquots on NMO
analyzer
Perform addi-
tional analyses
until RSD of
last three
injections
is <2%
Sample tank
analysis
Relative standard
deviation from
triplicate analysis
for NMO must be <2%
Analyze sample tank
after trap purging and
tank pressurization by
injecting aliquots on
NMO analyzer
Perform addi-
tional analyses
until RSD of
last three
injections is
                                                                                   O
                                                                                   O

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                                                               Section No.  3.17.6
                                                               Date May 31,  1991
                                                               Page 1
6.0   CALCULATIONS

      Calculation errors due to procedural or mathematical mistakes can be a part of
 total system  error.   Therefore,  it is  recommended  that  each set of calculations be
 repeated  or spotchecked,  preferably by a  team  member other than the  one  who  per-
 formed the original calculations.   If a difference greater than typical round-off
 error is  detected,  the calculations should be checked step-by-step until the source
 of error  is found and corrected.
      Calculations should be carried out to at least one extra decimal figure beyond
 that  of the acquired data  and should be  rounded off after final calculation to two
 significant  digits  for  each  run  or sample.   All rounding  of numbers should be
 performed in  accordance  with  the ASTM 380-76 procedures.   All calculations should
 then  be recorded on  a calculation form such as Figure 6.1.
      A computer program  is  advantageous  in reducing  calculation errors.    If  a
 computer  program is used, the  original data  entered  should  be included  in the
 printout  so  it can  be reviewed;   if differences are observed,  a new computer run
 should be made.  A  computer  program is  also useful  in maintaining a standardized
 format for reporting of  results.    It is highly  recommended  that  a standardized
 format including  the data shown in Figure 6.2  be  used  for reporting the emissions
 results.   The data  shown will allow auditing of the calculations.
      Table 6.1  at  the  end  of this  section  summarizes  the  quality  assurance
 activities for  calculations.

 6.1  Nomenclature
       The following nomenclature is used in the calculations:

       C   = TGNMO concentration of the effluent, ppm C equivalent.
       Cc  = Calculated  condensible organic  (condensate trap) concentration of the
             effluent, ppm C equivalent.
       Ccl) = Calculated  condensible  organic (condensate  trap)  blank concentration
             of the sampling equipment, ppm C equivalent.
       C   = Measured concentration (NMO analyzer) for the condensate trap ICV, ppm
             CO
               '2-
       C

       C

       C

       C

        L. m
             NMO.
       F   = Sampling flow rate, cc/min.
       L   = Volume of liquid injected, ul.
       M   = Molecular weight of the liquid injected, g/g-mole.
       mc  = TGNMO mass concentration of the effluent, mg C/dsm3.
cob= Measured blank  concentration (NMO analyzer)  for the condensate  trap
     ICV, ppm C02.
t  = Calculated noncondensible organic  concentration (sample tank) of  the
     effluent, ppm C equivalent.
tb = Calculated noncondensible organic blank concentration (sample tank)  of
     the sampling equipment, ppm C equivalent.
tm = Measured concentration  (NMO  analyzer)  for the sample tank,   ppm
     NMO.
tm = Measured blank concentration  (NMO analyzer) for  the  sample  tank,   ppm

-------
                                                               Section No.  3.17-6
                                                               Date May 31, 1991
                                                               Page 2
                                           o
       N   = Carbon number of the liquid compound injected  (N  =  12 for decane,  N =
             6 for hexane).
       Pf  = Final pressure of the intermediate collection vessel, mm Hg absolute,
       Pb  = Barometric pressure, cm Hg.
       Ptl = Gas sample tank pressure before sampling,  mm Hg absolute.
        Pt = Gas sample  tank  pressure after sampling,  but  before pressurizing,  mm
             Hg absolute.
       Ptf = Final gas sample tank pressure after pressurizing, mm Hg absolute.
        Tf = Final temperature of intermediate collection vessel, °K.
       Ttl = Sample tank temperature before sampling, °K.
        Tt = Sample tank temperature at completion of sampling, °K.
       Ttf = Sample tank temperature after pressurizing,  °K.
         V = Sample tank volume,  m3.
        Vt = Sample train volume, cc.
        Vv = Intermediate collection vessel volume,  m3.
        VB = Gas volume sampled,  dsm3.
         n = Number of data points.
         q = Total  number  of  analyzer  injections  of  intermediate  collection
             vessel during analysis (where k = injection number, 1 ... q).
         r = Total number of analyzer  injections of sample tank  during  analysis
             (where j = injection number, 1 ... r).
        XL = Individual measurements.
        x  = Mean value.                                                             x""X
        P  = Density of liquid injected, g/cc.                                       j    }
        0  = Leak check period, min.                                                 V,	/
       AP  = Allowable pressure change, cm Hg.

6.2  Calculations

     The following are the equations used with the example calculation form, Figure
6.1 to calculate the concentration  of  TGNMO,  the allowable limit for the pretest
leak check, and assess the efficiency of the condensate recovery system.

6.2.1   Allowable Pressure Change - Calculate  the allowable pressure change,  in cm
Hg, for the  pretest  leak check  using the following equation.   This value is then
compared  to  the actual  pressure change, in  cm Hg,  to  determine if  the  train is
suitable for sampling.
                                                                       Equation 6-1


6.2.2  Sample Volume - For  each  test run, calculate the  gas  volume sampled using
the following equation.
                          Vs = 0.3857 V
p      P
rt  _  rti
T7     T77
                                                                       Equation 6-2
6.2.3  Noncondenslble Organtcs  Concentration  -  For each sample tank, determine the
concentration of nonmethane organics, in ppm C,  using Equation 6-3.

-------
                                                               Section No.  3.17-6
                                                               Date May 31, 1991
                                                               Page 3
6.2.3  ffoncondensible  Organics  Concentration  -  For each sample tank,  determine the
concentration of nonmethane organics, in ppm C,  using Equation 6-3.
ptr
Ttf
Pt Ptl
Tt Ttl





1 V Cfc
— z_j tm
I* . *

                                                                       Equation 6-3
6.2.4    Noncondensible  Organics Blank  Concentration  -  For  blank sample  tank,
determine  the  concentration of  nonmethane  organics,  in ppm  C,  using Equation 6-3
and  the  values for  Ctnb.   The  blank value may  not exceed  5  PPm.  If the blank
value exceeds  5 ppm C, then the value of  5 PPm C may be  used  as the blank value.
The calculated blank value is C
                               t b
6.2.5  Condensible Organics Concentration - For each condensate trap, determine the
concentration of organics, in ppm C, using Equation 6-4.
                 cp = 0.3857
    q
i   Z
q  k=l
                                                cm.
                                                                       Equation 6-4
6.2.6  Condensible Organics Concentration - For each condensate trap, determine the
concentration of  organics,  in ppm C,  using Equation 6-4 and  the values for CCBb.
The blank value may  not exceed 15 ppm.  If the blank value exceeds 15 ppm C, then
the value of 15 ppm  C may be used as  the blank value.   The calculated blank value
is Ccb.

6.2.7   TGNMO Concentration  -  To determine the TGNMO concentration  for each test
run, use Equation 6-5.  NOTE:   The  method does not provide for blank correction.
The tester  must  have prior  approval  of the Administrator  to  use blank correction
(subtract blank).
                            = ct - ctb + cc - ccb
                                 Equation 6-5
6.2.8   TGNMO Mass  Concentration -  To determine  the  TGNMO mass  concentration as
carbon for each test run, use Equation 6-6.
                        m, = 0.4993 C
                                 Equation 6-6
                                                •  }

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                                                               Section No.  3.17.6
                                                               Date  May  31.  1991
                                                               Page  ^


6.2.9   Percent Eecovery -  Calculate  the percent recovery  for the  liquid  organic
injections   used  to  assess  the  efficiency  of  the  condensate recovery  and
conditioning  system using  Equation  6-7.    The  average  recovery  for  triplicate
injections shoul fall within 102 (of 100/0.
             Percent Recovery = 1.604 —  	  	
                                      L   P   Tf    N                   Equation  6-7
                                 \ v   •


6.2.10   "Relative Standard Deviation - Calculate  the  relative standard  deviation
(RSD) for the percent recoveries for triplicate injections of liquid organics  using
Equation 6-8.  The RSD should be less than 5% for each  set of triplicate analyses.
                                                                                   o
                               100  /^(Xi  - x)2
                         RSD = 	^ I  	                        Equation 6-8
                                ~ V    n - 1
                                x  »
                                                                                    O
                                                                                    o

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                                                                Section No.  3.17.6

                                                                Date May 31, 1991

                                                                Page 5
 F



 V.
                    ALLOWABLE PRETEST LEAK CHECK PRESSURE CHANGE




             cc/min,  Pb   =	.	cm Hg,    0  =	.  	 min,



                   cc
     AP = 0.01
                      =  	 .	cm Hg
                                                                        Equation 6-1



Si i-
I'
1.
V = 0. 	 m3, Ptl
Pti = 	 . 	 mm Hg, Tj =
K vs = 0.3857 V
/
Pt _ pti
Tt Ttl

                                    SAMPLE VOLUME



                                       =	.  	 mm Hg,



                                     	.  	 °K,   Tt







                                     =  0.
                                                             dsm3
                                                                              >K
                                                                        Equation 6-2
pti  "
Ttl





Ctml
          NONCONDENSIBLE ORGANICS CONCENTRATION




 mm Hg,   Pt   =	mm Hg,  Ptf  =	mm Hg,



      °K   T   -                °K    T    -                <
 •  __  *»•  A£      __ __ 	 >  	  *^  >  •'•tf  °~  	 	 —  * 	



	.  	 ppm NMO,  Ctm2  =	. 	 ppm NMO,




	 .  	 ppm NMO,  r =  	
                                                                           K,
                       tf
                   P    P
                   rt   rt
                   T    T
                   x    x
                                            *.
                                            tm
                                                   -	.  	 ppm C
                                                                        Equation 6-3
               Figure 6.1.  Calculation  form  for  Method 25 analysis.

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                                                                Section No.  3-17.6
                                                                Date May 31,  1991
                                                                Page 6
                                                                                    o
P'i  =
Lti
'tnbl
           NONCONDESIBLE  ORGANICS  BLANK CONCENTRATION

__ mm Hg,   Pt  =  ___  mm Hg,  Ptf  =

__ .  _ °K,  Tt  =  ___ . _ °K  ,  Ttf  =

 ___ .  _ ppm NMO,  Ctmb2  =  ___  . _ ppm NMO,

 ___ .  _ ppm NMO,  r =  _
                                                                     mm Hg,
      'tb
                    t t
                                                 =	. 	 ppm C
                                                                        Equation 6-3
                         CONDENSIBLE ORGANICS CONCENTRATION

Vv  =  0.	m3,  V.   =   0.	dsm3,

Pf  =	mm Hg,  Tf  =	. 	 °K,

      =	. 	 ppm C02 ,  Ccm2  =	.  	 ppm  C02 ,
                                                                                    O
 cm3
      =	. 	 ppm C02 ,  q  =
     Cc = 0.3857
                                    cm,.
                                                                        Equation 6-4
                                           =	.  	 ppm C
                               Figure 6.1.  Continued
                                                                                     O
                                               v  --1 -  -

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                                                               Section No.  3-17.6
                                                               Date May  31,  1991
                                                               Page 7
Vv  =  0.
 'crabl
                CONDENSIBLE ORGANICS BLANK CONCENTRATION

          	m3,  V8   =  0.	dsm3,

          	 mm Hg,  Tf  =	. _.°K,

          	. _ ppm C02 ,   Ccmb2  =	.  _ ppm C02

          	. 	 ppm C02,   q  =  	
                  V.
    Crh = 0.3857
     'cb
                                    cm
                             k=l
                                      bk
                                                                        Equation 6-4
                                      =	.  	 ppm C02
                                TGNMO CONCENTRATION

Ct  =	. 	 ppm C,  Ctb   =  	  . 	 ppm  C,   Cc   =	.  	 ppm C,

Ccb  =	. 	 ppm C
     c • ct ~ ctb*
cc " ccb   =	._ ppm C
C  =
                                                                  Equation 6-5

Note:  Blank subtraction requires prior  approval  of the  Adminstrator.

                        TGNMO MASS CONCENTRATION

	 . 	 ppm C
                mc = 0.4993
                	 . 	  mg C/dsm3
                                                                  Equation 6-6
                              Figure 6.1.  Continued

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                                                               Section No. 3.17.6
                                                               Date May 31, 1991
                                                               Page 8
                                  PERCENT RECOVERY

      	.	g/g-mole,  L  =	. 	 ul,

       	. 	 mm Hg,  Tf  =	. 	 °K,

Vv  =  0.	. m3 ,   p =  0.	kg/cc,

Ccm.=	. 	 ppm C,   N =	
             o
                                       pf  ccm
                           ^ I       V   J.   w III
      Percent Recovery = 1.604 —	  =	
                                       Tf   N
Equation 6-7
                            RELATIVE STANDARD DEVIATION
                                                 n  =
                      100
                RSD =
                               n - 1
Equation 6-8
              O
                               Figure 6.1.   Continued
                                                                                      O

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                                               FIELD DATA  AND  RESULTS  TABULATION
Plant:   XXXXXXXXXX

Sampling Location:  XXXXXXXXXX



Date

Run Start Time
Run Finish Time


Field Data

Sample Trap I.D.
Sample Tank I.D.
Sample Tank Volume,  V (n^)
Actual Volume Sampled,  V,  (dsm^*)
                        s

Field Initial Barometric Pressure, Pb (cm Hg)
Field Final Barometric  Pressure  (cm Hg)
                                                               Run  1      Run 2      Run 3      Blank     Audit  1     Audit  2
                                                             xx/xx/xx   xx/xx/xx   xx/xx/xx   xx/xx/xx   xx/xx/xx    xx/xx/xx
Field Initial Gauge Pressure  of Tank,
Field Final Gauge Pressure  of Tank
nk, Ptl
.  pt U
                                         (mm Hg absolute)
                                       mm Hg absolute)
Field Initial Temperature of Tank, Tt; (
Field Final Temperature of Tank, Tt (*K)
Laboratory Data

Final Tank Pressure,  Pfcf  (mm Hg absolute)
Final Tank Temperature, Ttf (°K)

Noncondenslble (tank)  Portion - Injection #1 (area units)
Noncondensible (tank)  Portion - Injection #2 (area units)
Noncondensible (tank)  Portion - Injection #3 (area units)
Instrument Blank (area units)
NMO Response Factor  (area units/ppm C)
•68°F -- 29.92 in.  Hg  (760 ran Hg)
                                                                                                                                  T) O C/5
                                                                                                                                  (0 {D 0>
                                                                                                                                  Oq rt O
                                                                                                                                  (D (D ft
(continued)
               Figure 6.2.  Recommended standard format for reporting Method 25  data and  results.
                                                                                                                                     U> O
                                                                                                                                     I-* •
                                                                                                                                       LO
                                                                                                                                     I-' •
                                                                                                                                     MD—J

                                                                                                                                        ON

-------
                                                                Run 1
                                                                           Run  2
                                                                                      Run  3
                                                                                                Blank
                                                                                                          Audit 1
                                                                                                                     Audit 2
                                                              xx/xx/xx   xx/xx/xx    xx/xx/xx   xx/xx/xx   xx/xx/xx   xx/xx/xx
Laboratory Data (Continued)

Volume of ICV, Vy (n3)
Final ICV Pressure,  P- (ran Hg absolute)
Final ICV Temperature. Tf (°K)

Condensible (trap) Portion - Injection fi (area units)
Condensible (trap) Portion - Injection #2 (area units)
Condensible (trap) Portion - Injection #3 (area units)
Instrument Blank (area units)
NMO Response Factor (area units/ppm C)
Results
Measured Concentration for Sample Tank, Ct  (ppra NMO)
Measured Concentration for Condensate Trap, C   (ppm C)

Noncondensible Organic Concentration (tank), Ct (ppra C)
Condensible Organic Concentration (trap), Cc (ppm C)
Note: Prior approval of Adninstrator required for blank substraction
TGNMO Concentration, C (ppn C)
Flue Gas Flow Rate
Emission Rate (rag/h)
••From EPA Method 	 testing.
                                                          Figure  6.2.   Continued
                                                                                                                                     *"0 t^ C/J
                                                                                                                                     03 p3 ro
                                                                                                                                     CD fl> ft
                                                                                                                                        VO—J
                                                                                                                                        (-» •
                                                                                                                                           ON
   O
o
o

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                                                               Section No.  3.17.6
                                                               Date May 31, 1991
                                                               Page 11
                 Table 6.1.   ACTIVITY MATRIX  FOR CALCULATION CHECKS
Characteristic
 Acceptance limits
Frequency and method
   of measurement
Action if
requirements
are not met
Analysis data
form
All data and calcu-
tions are shown
Visually check
Complete the
missing data
Calculations
Difference between
check and original
calculations should
not exceed round-off
error
Repeat all calcula-
tions starting with
raw data for hand
calculations;  check
all raw data input
for computer calcu-
lations; hand calcu-
late one sample per
test
Indicate errors
on calculation
form, Figure 6.1

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o
o
o

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                                                         Section No.  3.17-7
                                                         Date May 31,  1991
                                                         Page  1
 7.0     MAINTENANCE

     The  normal  use of emission testing equipment subjects it  to  corrosive  gases,
 extremes  in  temperature,  vibration,  and  shock.    Keeping the  equipment in  good
 operating order over an extended period of time requires knowledge of the equipment
 and  a  program of routine maintenance which is performed quarterly or  after  2830  L
 (100 ft3) of operation,  whichever is greater.  In addition to  the quarterly main-
 tenance,  a  yearly  cleaning  of pumps and metering  systems is recommended.   Main-
 tenance procedures  for the various components are  summarized in Table 8.1  at  the
 end  of the section.  The following procedures are not required,  but are recommended
 to increase  the reliability of the equipment.

 7.1  Pump

     Several  types  of  pumps  may be used to perform Method 25;  the two most  common
 are  the fiber vane  pump with in-line  oiler  and the  diaphragm  pump.   The fiber vane
 pump requires a  periodic  check of the oiler jar.  Its  contents  should be translu-
 cent; the oil should  be  changed if not translucent.  Use  the oil  specified  by the
 manufacturer.  If none is specified, use SAE-10 nondetergent oil.  Whenever a fiber
 vane pump starts to  run erratically or  during the  yearly disassembly,  the  head
 should be removed  and the fiber vanes  changed.   Erratic operation  of a diaphragm
 pump is normally due to either a bad diaphragm (causing leakage) or to malfunctions
 of the valves, which should be cleaned annually by complete disassembly.

 7.2  Rotameter

     Rotameters should be disassembled  and  cleaned  according  to the  manufacturer's
 instructions  using  recommended  cleaning fluids  every 3  months  or upon erratic
 operation.

 7.3  Manometer

     The fluid in the  manometers should be  changed  whenever there is discoloration
 or visible matter in the fluid, and during the yearly disassembly.

 7.^  Sampling Train

     All  remaining  sampling train  components  should be visually checked every  3
 months and  completely disassembled and cleaned or replaced  yearly.   Many  items,
 such as quick disconnects, should  be  replaced  whenever  damaged  rather than checked
 periodically.  Normally,  the best procedure for maintenance in the field is to have
 on hand another  entire sampling system,  including  a pump, probe, U-tubes,  filter
 holders,   sample  tanks, and  heated  sample  line rather than replacing individual
 components.    It is recommended  that the  U-tubes  be  filled  with  nitrogen after
burnout to reduce oxidation of the metal surface.   The sample  tanks should be clean
 and dry when being stored between tests.

 7.5  Gas Chroroatograph and NDIR

     Maintenance activities and schedules for gas  chromatographs and  NDIRs are make
 and  model specific.   It  is  recommended  that the  analyst consult  the operator's
manual for instructions relative to maintenance practices  and  procedures.

-------
                                           Section No. 3-17.7
                                           Date May 31, 1991
                                           Page  2
Table 7.1.  ACTIVITY MATRIX FOR EQUIPMENT MAINTENANCE CHECKS
o

Apparatus
Fiber vane
pump
Diaphragm
pump
Rotameter
Manometer
Sampling
train
components
Gas chroma-
tograph and
NDIR

Acceptance limits
In-line oiler
free of leaks
Leak- free valves
functioning properly
Clean and no errat-
ic behavior
No discoloration or
visible matter in
the fluid
No damage
See owner's manual

Frequency and method
of measurement
Periodically check
oiler jar; remove
head and change fiber
vanes
Clean valves during
yearly disassembly
Clean every 3 mo. or
whenever ball does
not move freely
Check periodically
and during disassem-
bly
Visually check every
3 mo.; completely
disassemble and
clean or replace
yearly
See owner's manual

Action if require-
ments are not met
Replace as
needed
Replace when
leaking or mal-
functioning
Replace
Replace parts
as needed
If failure noted,
replace appro-
priate components
See owner's manual
                                                                      O
                                                                      o

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                                                            Section No.  3-17-8
                                                            Date May 31, 1991
                                                            Page 1
8.0     AUDITING PROCEDURES
      An  audit  is an  independent assessment  of data  quality.   Independence  is
 achieved  if  the individual(s)  performing  the audit  and  their  standards  and
 equipment  are  different  from  the  regular field  team  and  their  standards  and
 equipment.   Routine  quality assurance  checks by  a  field team  are necessary  to
 generate good  quality data, but they are not part of the auditing procedure.   Table
 8.1  at  the  end  of  this  section  summarizes  the quality  assurance functions  for
 auditing.
      Based on  the requirements of Method 25 and the results of  collaborative test-
 ing  of other EPA Test Methods,  one performance audit is  required when  testing for
 compliance for  Standards  of New Source  Performance  (and as  required by  other
 government agencies)  and  is recommended when testing for other purposes;   and  a
 second performance audit is recommended.  The two performance  audits are:
      1.  An  audit of the  sampling and  analysis of  Method 25 is  required  for NSPS
         and recommended for other purposes.
      2.  An  audit of the data processing is recommended.
      It  is suggested  that  a  systems  audit be  conducted  as specified by  the quality
 assurance  coordinator in addition to these performance audits.  The two  performance
 audits and the systems audit are  described in detail in Subsections 8.1  and 8.2,
 respectively.

 8.1   Performance  Audits

      Performance  audits are  conducted  to  evaluate quantitatively the  quality of
 data produced  by the  total measurement  system (sample collection, sample analysis,
 and  data processing).   It is required that   a cylinder  gas  performance  audit be
 performed  once during every  NSPS test utilizing Method  25 and  it  is  recommended
 that a  cylinder  gas  audit be performed once  during any enforcement  source test
 utilizing  Method  25 conducted under regulations other than NSPS.

 8.1.1  Performance Audit of  the Field Test  -  As stated in Section 4.5 of Method 25
 (40  CFR 60,  Appendix  A)   and the "Instructions for  the  Sampling and  Analysis of
 Total  Gaseous  Nonmethane Organics  from  Quality Assurance  Audit  Cylinders using EPA
 Method 25  Procedures" (supplied with the EPA  audit  gas  cylinders), a  set  of two
 audit  samples  are to be  collected in the field (not laboratory) from two different
 concentration  gas cylinders  at the same time  the compliance test samples are being
 collected.  The two audit  samples are then analyzed concurrently and in exactly the
 same  manner  as   the  compliance  samples  to evaluate the  tester's and analyst's
 technique and  the instrument calibration.  The information required to document the
 collection and analysis of the audit  samples has  been included  on the example data
 sheets shown later in  Figures 8.1 and 8.3-   The  audit  analyses shall agree  within
 20 percent of the actual cylinder concentrations.
     The operator of  the  affected  facility  is  responsible  for  informing  local,
 state,  and  federal   agencies  of  the  test  program  and  of  the  test  schedule.
 Therefore,  the operator of the affected facility is  responsible  for requesting (and
 handling of)   the audit samples  from  the  agency  responsible  for observing  the
 compliance test.  The tester is  responsible  for informing  his  client of  the details
 of any method used and any audit  samples  required to  validate the compliance test.
These  details  are  usually  part  of  a  pretest meeting,   but  many  times pretest
 meetings are  not  necessary  depending  on  the scope of  the  work  and  permit
 requirements.

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                                                            Section No.  3.17-8
                                                            Date May 31, 1991
                                                            Page 2                  • x—v

     The facility  (or  tester)  may obtain audit cylinders by  contacting the agency  —
responsible for observing  and/or evaluating the compliance test  and  informing the
agency the time and location of  the  compliance  test.   This  should be done at least
l5  days prior  to  the  test  date.    The  responsible  agency  will  contact:  U.S.
Environmental  Protection  Agency,  Atmospheric  Research  and  Exposure  Laboratory,
Quality Assurance  Division (MD-77),  Research Triangle Park,  North Carolina 277H
and have the cylinders shipped to the specified site.

     Responsibilities  of the Audit  Supervisor  -  The  primary  responsibilities  of
the audit supervisor are to ensure that  the proper audit gas  cylinders  are ordered
and safe-guarded,  and to interpret the results obtained by the analyst.
     When notified by the testing company 'that a test is to be conducted, the audit
supervisor  will order  the  proper  cylinders  from the EPA's  Quality  Assurance
Division.    Generally  the  audit  cylinders  will  be  shipped  (at  EPA's  expense)
directly to the specified  site.   However,  if the  audit  supervisor  will be on-site
during  the  compliance  test,  the  audit  cylinders  may be  shipped  to  the  testing
company for transport  to the  sampling site.   Since the  audit cylinders are sealed
by  EPA,  the testing  firm will  not  be  allowed to collect any audit  gas  without
breaking the seal.   The audit gas concentration^)  should  be in the range of 50/»
below to 100% above  the applicable standard.    If  two  cylinders are not available,
then one cylinder can be used.
     The audit supervisor must ensure that the audit gas cylinder(s) are shipped to
the correct address,  and  to  prevent vandalism, verify  that  they are  stored  in a
safe location both before and after  the audit.  Also,  the audit cylinders should
not be analyzed when  the pressure drops below  200  psi.   The  audit1 supervisor then
ensures that the audits are conducted as described below.  At  the conclusion of the
collection  of  the  audit  samples,  the  cylinders  are then  returned  to  shipping
laboratory as per  the instructions supplied with the  cylinders  at the expense of
the  facility.   If the  tester  is to transport  the  audit cylinders  to his  home
laboratory for shipment  back  to the EPA/QAD contractor,  the  audit supervisor will
seal both cylinders to ensure  that additional audit sample  gas cannot be collected
without breaking the seal.
     The audit  supervisor must  also interpret the  audit results.   Indication of
acceptable results  may be obtained  immediately by reporting the audit compliance
test results in ppm by telephone to the responsible enforcement agency.   The tester
must also include  the  results  of both audit samples,  their identification numbers,
and  the analyst's  name along  with   the results  of  the compliance  determination
samples in  the  appropriate reports  to the  EPA regional  office  or the  appropriate
enforcement agency during the 30-day period.
     When the measured concentration agrees within 20% of the true value, the audit
results are considered acceptable.   Failure  to meet  the 20-percent specification
may  require  reanalysis  of   the audit samples  and  compliance  test  samples,
reauditing, or  retests  until  the audit problems are  resolved.   However,  if the
audit results do not affect the  compliance  or noncompliance status of the affected
facility,  the Administrator  (enforcement agency)  may waive  the reanalysis, further
audits, or retest requirements and accept the results  of the  compliance test.  For
example, if the  audit results average 38.6%  low, the compliance results  would be
divided by  (1  -  0.386)  to determine  the correlated effect.   If  the  audit results
average 58.3% high,  the  compliance sample  results would  be divided  by  (1 + 0.583)
to determine the effect.  When the compliance status of the source is the same with
and  without  the  correlated  value,  then  the  responsible  agency  may   accept  the
results of the  test.    While  steps  are  being  taken  to  resolve audit  analysis
problems,   the  Administrator  may  also choose  to use  the  data  to determine  the
o
o

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                                                            Section No.  3-17.8
                                                            Date May 31,  1991
                                                            Page 3

compliance or noncompliance of the affected facility.
     The  same  analysts,  analytical reagents,  and  analytical system shall be used
for the compliance samples and the EPA audit samples;  if this condition is met,  and
the same  testing firm is collecting other sets of compliance  samples,  auditing of
subsequent compliance  analyses  for the same  enforcement  agency within 30 days is
not required.   An audit sample set may not  be used to validate  different sets of
compliance samples under the jurisdiction of different enforcement agencies, unless
prior arrangements are made with both enforcement agencies.
     During  the  audit,  the  audit supervisor should  record  the  coded  cylinder
number(s) and  cylinder pressure(s) on  the "Audit Report"  form,  Figure 8.1.    The
individual being audited must not be told the actual audit concentrations or the
calculated audit percent accuracy.
     On-site Collection  of Audit  Sample(s)  - The  cylinder gas  performance  audit
must be  conducted in  the  field  (not laboratory) at  the  same  time  the  compliance
test samples are  being taken. A  maximum of 5L of audit gas  is  to be used for each
test run  unless  multiple  tanks  are  required for  sampling.   The  tester will be
required  to  supply  a two-stage regulator  (CGA -  350),  a glass manifold  or Teflon
tee connection and other suitable Swagelok fittings (they are not supplied) for use
with the  audit gas cylinder. The  recommended  procedures for conducting the on-site
audit sample collection are as follows:
     1.   The audit supervisor  (agency representative)  should verify that  the seal
         affixed by  shipping  or  supplying laboratory is  still intact.   After the
         seal has been checked by the  audit  supervisor,  the tester may  break the
         seal.   However, if the audit supervisor is not present at the time of the
         audit, the tester may break the seal and proceed with the audit.
     2.   The tester should set up the Method 25 sampling train and perform the leak
         check.
     3.   The audit gas from the cylinder has  to be  sampled  at atmospheric pressure
         either from a glass manifold or through a Teflon tee connection.   This can
         be  done  by attaching both  the cylinder  and the  probe  of the  Method 25
         sampling train to two of  the manifold or  tee connections while excess gas
         flows  out through  the remaining  connection as shown in  Figure 8.2.   This
         can be accomplished by starting the cylinder gas flow into the manifold or
         tee with the  sampling train  flow turned off.  Then,  turn  on  the sampling
         train  flow  while adjusting  the  flow from the  audit cylinder  to  ensure
         excess audit gas flow from the manifold or tee.   After the proper sampling
         flow rate has been obtained in the sampling train,  adjust the audit cylin-
         der so only a few  cubic centimeters of excess gas is discharged from the
         manifold or tee.  The tester must ensure that the audit gas is conserved.
     4.   Use the same  sampling flow  rate  and sample volume  as  used for field test
         samples.  When  a constant flow  rate can no  longer be  maintained by the
         sampling train, it should be turned off and then  the  audit cylinder shut
         off.  Ensure  that  the audit cylinder is closed  tight  to prevent leakage.
         If  the  compliance  test  requires more than one  sample tank to  complete a
         run, the audit should use the same number of tanks  required by the average
         run.
     5.   The same procedures  are  repeated for the second  audit cylinder using"a
         separate sampling train.
     6.   The sampling  trains  containing  the  audit  samples should  be stored  and
         shipped in the same manner as and along with  the  field test samples.
     7.   In  all cases,  it is recommended that the audit supervisor reseal the  audit
         cylinders to ensure no tampering.  However, if the test  firm  is  to return
         the cylinder to shipping or supplying laboratory, it is mandatory that the

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o
                                                            Section No.  3.17-8
                                                            Date May 31, 1991
                                                            Page 4

         audit cylinders are resealed by the audit supervisor.
     8.  The audit cylinders  are  to be returned immediately after  the  test  to the
         EPA/QAD contractor at  the  cost of the facility  (or tester if  applicable)
         either by ground transportation or air cargo.  They are not to be shipped
         collect.

     Analysts of Audit Sample(s) - Analyze the  collected audit  sample fractions
(condensibles and  noncondensibles)  at  the  same time as  the Method  25 compliance
test samples.   Follow the procedures described in the method  for sample analysis,
calibration,  and  calculations.    The  same   analysts,  analytical  reagents,  and
analytical system  shall  be used,for b9th  the  compliance test  samples  and the EPA
audit samples.
     Reporting  of  Audit  Sample(s)  Results -  The reporting of the  audit results
should be  the  responsibility  of the tester  to ensure taht the data is acceptable
and valid.  The audit sample  results are to be reported  to the responsible agency
by  the  testing  firm  in  terms  of  condensibles (U-trap  fraction),  noncondensibles
(tank fraction), and total (sum of both fractions) as parts-per-million carbon (ppm
C).    The  agency will in  turn  report  the  results  to  the EPA/QAD  contractor for
continuing evaluation of the Method 25 audit  program.   Additionally,  the  tester
must supply  document  in the test  report,  the  results  of both audit  samples  as
described  above,  their identification  numbers, and  the analyst's  name along with
the results of  the compliance determination samples.  The operator of the affected
facility is responsible  for the dissemination  of  any compliance sample  results and
the correct distribution of reports to the EPA regional office or the  appropriate
enforcement agency during the 30-day period for which the audit samples represent.    (i

8.1.2  Performance Audit of Data  Processing - Calculation  errors  are prevalent in
processing data.  Data processing errors can be determined by auditing the recorded
data on  the  field and laboratory forms.   The original and audit (check)  calcula-
tions should agree within round-off error;  if not, all of the remaining data should
be  checked.   The  data  processing  may  also  be audited  by providing  the testing
laboratory with  specific data sets  (exactly as would appear in the field),  and by
requesting that  the data calculation be completed and that the results  be returned
to the agency.   This  audit is useful in checking  both computer programs and manual
methods of data processing.

8.2  Systems Audit

     A systems  audit  is  an on-site,  qualitative inspection and review of the total
measurement  system  (sample   collection,  sample  analysis,  etc.).   Initially,  a
systems  audit  is recommended for each  enforcement source test, defined here as a
series of  three  runs  at  one source.   After the test team gains experience with the
method, the frequency of auditing may be reduced — for example, to once every four
tests.
     The auditor should have extensive background experience  in  source sampling,
specifically  with  the  measurement   system  being  audited.   The functions  of the
auditor are summarized below:
     1.  Inform  the  testing team of the results  from previous audits, specifying
         any area(s) that need special  attention or improvement.
     2.  Observe procedures and techniques  of  the field team during sample collec-
         tion.
     3.  Check/verify  records of  apparatus calibration checks  and quality control
         used in the laboratory analysis  of control samples  from previous source

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                                                            Section No.  3.1?.8
                                                            Date May 31,  1991
                                                            Page 5

         tests, where applicable.
     4.  Record the  results of  the  audit,  and forward  them  with comments  to  the
         test  team  management  so  that  appropriate  corrective  action  may  be
         initiated.
     While on  site,  the auditor observes the source  test team's  overall  perfor-
mance, including the following specific operations:
     1.  Setting up and leak testing the sampling train.
     2.  Collecting the sample at a constant rate at the specified flow rate.
     3.  Conducting the final leak check and recovery of the samples.
     4.  Sample  documentation  procedures,   sample  recovery,  and  preparation  of
         samples for shipment.
Figure 8.3 is a suggested checklist for the auditor.

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                                                       Section No.  3.17-8
                                                       Date Hay 31,  1991
                                                       Page 6
                              AUDIT REPORT
O
Part A. - To be filled out by organization supplying audit cylinders.
          1. Organization supplying audit sample(s)  and shipping address

          2. Audit supervisor, organization, and phone number

          3. Shipping instructions: Name, Address, Attention

          4. Guaranteed arrival date for cylinders -	'
          5. Planned shipping date for cylinders -
          6. Details on audit cylinders from last analysis




d. Audit gas (es) /balance gas..
f . Cylinder construction. .....

Low cone.



N2
Aluminum

High cone



N2
Aluminum

Part B. - To be filled out by audit supervisor.
          1. Process sampled 	
             Audit location
2.
3-
             Name of individual audit
             Audit date
 O
          5. Audit cylinders sealed
          6. Audit results:




d. Measured concentration, ppm C


e. Actual audit concentration, ppm C
f. Audit accuracy:1

Percent accuracy1 =
Measured Cone. - Actual Cone. x 100
Actual Cone.
g. Problems detected (if any) 	 	

Low
cone.
cylinder











High
cone.
cylinder











          1The audit accuracy is calculated on the total concentration only.
                  Figure 8.1.  Field audit report form.
 O

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                                                                   Section No. 3.17.8
                                                                   Date May 31, 1991
                                                                   Page 7
                                                                          MANOMETER
                                 EXCESS
                                  FLOW
                                                                 FLOW
                                                               CONTROL
                                                                VALVE
                   ROTAMETER
                                               ROTAMETER
                             TEFLON TEE"
                             OR MANIFOLD
                                                                          4-
SAMPLE
 TANK
 VALVE
                                                          CONDENSATE
                                                              TRAP
       SAMPLE
         TANK
                     AUDIT
                   CYLINDER
(in
>|Lj
                          Figure 8.2.   Schematic of Method 25 audit system.

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                                                 Section No. 3.17-8
                                                 Date May 31. 1991
                                                 Page 8
o
Yes




















1 v




No

























Comments

























Operation
PRESAMPLING PREPARATION
1. Knowledge of process operations
2. Calibration of pertinent equipment, in
particular, temperature readouts and flowmeters
3. Selection and checkout of equipment for proper
sampling techniques
ON-SITE MEASUREMENTS
* 4. Sampling system properly assembled
5. ^Sampling system leak check acceptable
6. Sample probe and filter at proper temperature
7. Sample system purged properly
8. Constant rate sampling properly conducted
9. Heater systems maintained at proper temperatures
10. Proper number of samples & sampling time
11. Recording of pertinent process conditions during
sample collection, samples properly identified,
and calculations properly conducted
POSTSAMPLING
12. Results of audit (+ 20% or other value)
13. Oxidation catalyst efficiency test acceptable
14. Reduction catalyst efficiency test acceptable
15. NMO linearity and calibration test acceptable
16. C02 linearity and calibration test acceptable
17. NMO analyzer performance test acceptable
18. Condensible organic recovery system leak check
19. System background test acceptable
20. Temperature, volumes, pressures, and concen-
trations properly recorded
21. Analytical results properly calculated

COMMENTS
                                                                         O
Figure 8.3.  Method 25 checklist to be used by auditors.
                                                                          O

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                                                            Section No.  3.17-8
                                                            Date May 31, 1991
                                                            Page 9
              Table 8.1.   ACTIVITY MATRIX  FOR AUDITING PROCEDURES
Apparatus
Performance
audit of
analytical phase
 Acceptance limits
Measured relative
error of audit
samples less than
20% for both samples
Frequency and method
   of measurement
Frequency: Once during
every enforcement
source test*
Method; Measure audit
samples and compare
results to true values
Action if
requirements
are not met
Review operating
technique and
repeat audit,
repeat test,
reject test, or
accept results
Data processing
errors
Original and checked
calculations agree
within round-off
error
Frequency: Once during
every enforcement
source test*
Method; Independent
calculations starting
with recorded data
Check and correct
all data from the
audit period
represented by
the checked data
Systems audit—
observance
of technique
Operational tech-
nique as described
in this section of
the Handbook
Frequency; Once during
every enforcement
source test* until
experience gained,
then every fourth
test
Method; Observation of
techniques assisted
by audit checklist,
Figure 8.3
Explain to test
team their devia-
tions from rec-
commended tech-
niques and note
on Fig. 8.3
*As defined here, a source test for enforcement of the NSPS comprises a series of
 runs at one source.  Source tests for purposes other than enforcement of NSPS may
 be audited at the frequency determined by the applicable group.

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o
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                                                              Section No. 3.17-9
                                                              Date May  31, 1991
                                                              Page 1
9.0     RECOMMENDED  STANDARDS  FOR  ESTABLISHING TRACEABILITY

     To  achieve  data  of  desired  quality,   two essential  considerations  are
 necessary:  (1)  the  measurement process  must be in a state of statistical  control
 at the time of the  measurement,  and (2)  the systematic  errors,  when  combined with
 the random variation   (errors  or  measurment),   must   result  in  an  acceptable
 uncertainty.   As evidence  in support of  good quality  data, it is necessary to
 perform  quality  control  checks and  independent  audits of the  measurement process;
 to document these  data;  and  to  use  materials,  instruments,  and  measurement
 procedures  that can be traced to an  apropriate standard of reference.
     Data must be routinely obtained  by  repeat  measurements of  standard reference
 samples  (primary, secondary, and/or working standards)  and the establishment of a
 condition   of  process  control.    The  working calibration  standards  should  be
 traceable to standards  of higher accuracy.  It is recommended,  but  not required,
 that the analyst use a NBS-SRM for propane  to make the analysis traceable to an NBS
 Standard Reference Material.
     Audit  samples  (as discussed  in Section 3.17.8) must  be used to  validate test
 results  for  compliance  determination  purposes  and  are   recommendeed   as  an
 independent  check on the measurement process when  the method is performed for other
 purposes.   This makes all  the compliance  determination samples traceable  to the
 same audit source at EPA.

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                                                               Section No.  3.17.10
                                                               Date May 31,  1991
                                                               Page 1
10.0 REFERENCE  METHOD
               Method 25 - Determination of Total Gaseous NonMethane
                            Organic Emissions as Carbon

 1.   Applicability and Principle

     1.1  Applicability.  This method applies to the measurement of volatile organic
 compounds  (VOC)  as total gaseous  nonmethane  organics (TGNMO) as  carbon  in source
 emissions.    Organic  particulate  matter  will  interfere with  the analysis,  and,
 therefore,  a particulate  filter is required.   The minimum detectable concentration
 for  the method is 50 ppm as carbon.
     When  carbon dioxide  (C02)  and water vapor are present  together  in the stack,
 they can produce a  positive  bias in the sample.   The magnitude of the bias depends
 on  the concentration of  C02  and  water  vapor.   As  a guideline,  multiply  the C02
 concentration,  expressed  as volume  percent,  times the  water vapor concentration.
 If this product  does not exceed  100, the bias can be considered insignificant.  For
 example,  the bias  is  not significant for  a source having  10 percent C02  and 10
 percent water vapor,  but it would be  significant for a source  near the detection
 limit  having 10  percent C02 and  20 percent water vapor.
     This  method is not the only  method that  applies  to the measurement of TGNMO.
 Costs,  logistics,  and other practicalities  of source testing may make other test
 methods  more desirable  for measuring  VOC contents  of certain  effluent streams.
 Proper judgment is required  in determining the  most applicable  VOC  test method.
 For  example, depending upon the molecular weight of the organics in the effluent
 stream,  a  totally  automated   semicontinuous  nonmethane  organics  (NMO)  analyzer
 interfaced  directly to the source may  yield accurate results.   This approach has
 the  advantage of providing  emission data  semicontinuously  over  an  extended time
 period.
     Direct measurement  of  an  effluent with  a  flame  ionization  detector  (FID)
 analyzer  may be appropriate with prior  characterization  of  the gas  stream and
 knowledge  that  the detector responds predictably to the organic compounds in the
 stream.  If present,  methane (CHA) will,  of course,  also be measured.  The FID can
 be  applied to the  determination of the mass concentration  of the total molecular
 structure  of the organic emissions under  any  of  the following limited conditions:
 (1)  where  only  one compound  is  known  to exist; (2)  when  the  organic compounds
 consist  of  only  hydrogen and  carbon;  (3) where  the relative percentages  of the
 compounds  are known or can be  determined,  and the FID  responses to the compounds
 are  known;  (4)  where  a consistent mixture of the compounds exists before and after
 emission control and only the  relative  concentrations are to be assessed;  or (5)
 where  the  FID can  be calibrated  against  mass standards of  the  compounds emitted
 (solvent emissions, for example).
     Another example of the use  of a direct FID is as a  screening  method.  If there
 is  enough  information available to  provide  a   rough  estimate  of  the analyzer
 accuracy,   the  FID  analyzer can be  used  to determine  the  VOC  content  of  an
 uncharacterized  gas stream.    With  a  sufficient buffer  to account  for possible
 inaccuracies,  the direct FID can be a useful  tool  to  obtain  the desired results
 without  costly  exact  determination.    In  situations  where  a  qualitative/
 quantitative analysis of  an   effluent  stream  is   desired  or  required,   a  gas
 chromatographic  FID system  may  apply.    However, for  sources  emitting numerous
 organics, the time  and expense of  this approach will be  formidable.
                                                               1

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                                                               Section No.  3.17.10
                                                               Date May 31.  1991
                                                               Page 2
o
     1.2 Principle.  An  emission sample is withdrawn from the stack  at a constant
rate through a heated filter and a chilled condensate trap by means of an evacuated
sample   tank.     After  sampling  is  completed,   the  TGNMO are determined  by
independently analyzing the condensate trap and sample tank fractions  and combining
the analytical  results.   The  organic content of  the condensate trap  fraction  is
determined by oxidizing  the NMO to C02 and quantitatively collecting the effluent
in an evacuated vessel; then a portion of the C02  is reduced to CHA and measured  by
an FID.  The organic content of the sample tank fraction is measured by injecting a
portion  of  the  sample  into a  gas  chromatographic  column to  separate  the NMO from
carbon monoxide  (CO).  C02.  and CH/,;  the  NMO  are  oxidized to C02.  reduced to CHA.
and measured by an  FID.    In  this  manner,  the  variable  response  of the FID
associated with different types of organics is eliminated.

2.  Apparatus

     2.1 Sampling.  The sampling system consists of a heated probe, heated filter,
condensate  trap,  flow  control system,  and sample  tank  (Figure  25~1).   The  TGNMO
sampling equipment  can be  constructed  from commercially available components and
components fabricated in a machine shop.  The following equipment is required:

     2.1.1 Heated Probe.   6.4-mm (1/4-in.) OD stainless steel tubing with a heating
system capable of maintaining  a gas temperature at the exit  end  of at least  129°C
(265°F).   The probe shall  be equipped  with a thermocouple at  the exit end  to
monitor the gas temperature.                                                       x""N.
       A suitable probe  is  shown in  Figure 25~1•   The nozzle is  an  elbow f ittingf  A
attached to  the  front  end  of  the  probe while the  thermocouple is  inserted in the\__y
side arm of a tee fitting attached to the rear of  the probe.  The probe is wrapped
with a suitable  length of high temperature heating tape,  and then covered with two
layers of glass cloth insulation and one layer of aluminum foil.
     NOTE;  If  it is not possible  to use  a heating system for safety reasons,  an
unheated system with an in-stack filter is a suitable alternative.

     2.1.2 Filter Holder.   25-mm (15/l6-in.) ID Gelman filter holder with stainless
steel body  and stainless steel support screen with the Viton 0-ring  replaced by a
Teflon 0-ring.
     NOTE;    Mention of  trade  names  or specific products  does not  constitute
endorsement by the Environmental Protection Agency.

     2.1.3 Filter Heating System.  A metal box consisting of an inner and an outer
shell separated  by  insulating material with  a heating element in  the inner  shell
capable of maintaining a gas temperature at the filter of 121 +_ 3°C (250 +_ 5°F).
     A suitable  heating  box is shown in  Figure 25-2.  The outer  shell  is a  metal
box that measures 102 mm x  280 mm x 292 mm (4 in.  x 11 in. x  11 1/2 in.), while the
inner shell is a metal box  measuring 76 mm x 229 mm x 2*41 mm  (3 in. x 9 in. x 9 1/2
in.).   The inner box is supported by 13-mm (1/2-in.) phenolic rods.  The void space
between  the boxes is filled with fiberfrax insulation which  is  sealed in place  by
means of a  silicon  rubber bead around the upper sides of the box.  A  removable lid
made in  a  similar manner,   with a  25-mm (1-in.)  gap between  the  parts,  is used  to
cover the heating chamber.
     The  inner  box  is heated with  a 250-watt  cartridge heater, shielded  by  a f~\
stainless  steel  shroud.    The heater is  regulated by a  thermostatic temperaturef
controller  which is  set to maintain  a  temperature of  121° C  as measured  by  a
thermocouple in the gas line just before the filter.  An additional thermocouple  is

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                                                               Section  No.  3.17.10
                                                               Date May 31, 1991
                                                               Page 3
 used  to monitor  the  temperature of the gas behind the filter.
      2.1.4  Condensate Trap.   9.5-mm  (3/8-in.)  OD 316  stainless  steel tubing bent
 into  a U-shape.   Exact dimensions  are  shown in Figure 25-3.   The tubing shall be
 packed with coarse  quartz wool,  to  a density  of approximately  0.11 g/cc before
 bending.   While the  condensate  trap  is packed  with  dry ice in  the Dewar, an ice
 bridge may form between  the  arms  of the  condensate trap making it difficult to
 remove the condensate trap.   This problem  can be prevented by  attaching a steel
 plate between the arms  of the  condensate  trap in the same plane  as the arms to
 completely  fill the intervening  space.

      2.1.5  Valve.   Stainless  steel shut-off valve for starting and  stopping sample
 flow.

      2.1.6  Metering Valve.  Stainless steel  control valve for regulating the sample
 flow  rate through the sample  train.

      2.1.7  Rotameter.    Glass  tube  with  stainless  steel  fittings, capable of
 measuring sample flow in  the  range  of 60 to  100  cc/min.

      2.1.8  Sample Tank.   Stainless steel or aluminum tank with a  minimum  volume of
 4 liters.

      2.1.9  Mercury Manometer or Absolute  Pressure  Gauge.   Capable of  measuring
 pressure to within 1  mm Hg in the range of 0 to  900 mm.

      2.1.10 Vacuum  Pump.    Capable  of  evacuating to  an  absolute  pressure of 10 mm
 Hg.

      2.2.   Condensate Recovery Apparatus.   The  system for  the  recovery of the
 organics  captured in the  condensate  trap  consists  of  a heat  source,   oxidation
 catalyst,  nondispersive  infrared  (NDIR)  analyzer  and an  intermediate collection
 vessel  (ICV).  Figure 25-4  is a  schematic of a typical  system.  The  system shall be
 capable  of proper  oxidation and  recovery,  as specified  in  Section  5«1.   The
 following major components  are required:

     2.2.1    Heat  Source.    Sufficient  to heat  the  condensate  trap   (including
 connecting  tubing) to a temperature of 200°C.   A  system  using  both a heat gun and
 an electric tube furnace  is recommended.

     2.2.2  Heat Tape.  Sufficient  to  heat  the connecting tubing between  the water
 trap and the oxidation catalyst  to 100°C.

     2.2.3.  Oxidation Catalyst.  A suitable length of 9.5-mm (3/8-in.) OD Inconel
 600  tubing packed  with  15 cm  (6  in.) of 3.2-mm  (1/8-in.)  diameter  19 percent
 chromia on  alumina pellets.  The catalyst material is  packed in  the center of the
 catalyst tube  with quartz  wool  packed on  either end  to hold it in place.   The
 catalyst tube shall be mounted vertically in a 650°C  tube furnace.

     2.2.4  Water  Trap.   Leak  proof,  capable  of  removing moisture  from the gas
stream.

     2.2.5  Syringe Port.   A 6.4-mm (1/4-in.) OD stainless steel tee fitting with a

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                                                               Section No.  3.17.10
                                                               Date May 31,  1991
                                                               Page 4
rubber septum placed in the side arm.
     2.2.6 NDIR Detector.  Capable of  indicating  C02  concentration in the range of
zero to 5 percent,  to monitor the progress of combustion  of the organic compounds
from the condensate trap.

     2.2.7 Flow-Control Valve.   Stainless  steel,  to maintain the trap conditioning
system near atmospheric pressure.

     2.2.8 Intermediate  Collection Vessel.   Stainless steel  or aluminum, equipped
with a female  quick connect.   Tanks  with nominal volumes  of  at least 6 liters are
recommended.     \       r
     2.2.9  Mercury Manometer  or Absolute  Pressure Gauge.
pressure to within 1 mm Hg in the range of 0 to 900 mm.
                                                              Capable  of  measuring
     2.2.10 Syringe.   10-ml gas-tight,  glass syringe equipped  with an appropriate
needle.                                         •""•'

     2.3  NMO  Analyzer.     The  NMO  analyzer  is   a gas  chromatograph   (GC)  with
backflush capability  for  NMO analysis and is equipped with  an  oxidation catalyst,
reduction catalyst, and FID.  Figures 25-5 and 25-6 are schematics of a typical NMO
analyzer.  This semicontinuous  GC/FID analyzer  shall be  capable of: (1)  separating
CO, C02 , and CH4  from NMO,  (2)  reducing the  C02 to CHA  and quantifying as CH^,. and
(3) oxidizing  the NMO to  C02,  reducing the C02  to CH4  and quantifying  as CH4.
according to Section 5-2.  The analyzer consists of the following major components:

     2.3.1  Oxidation Catalyst.   A suitable length of 9.5-mm (3/8-in.)  OD Inconel
600 tubing  packed with 5-1 cm  (2 in.)  of 19  percent chromia  on 3«2-mm (1/8-in.)
alumina  pellets.    The  catalyst material  is  packed  in  the center  of the tube
supported  on  either  side  by quartz  wool.    The  catalyst   tube  must  be  mounted
vertically in a 650°C  furnace.

     2.3.2   Reduction Catalyst.   A 7.6-cm  (3-in.)  length of  6.4-mm  (1/4-in.)  OD
Inconel  tubing fully packed with 100-mesh pure nickel powder.   The catalyst tube
must be mounted vertically  in a 400°C furnace.

     2.3.3   Separation Column(s).   A 30-cm  (1-ft)  length of  3.2-mm  (1/8-in.)  OD
stainless steel tubing packed with 60/80 mesh  Unibeads IS followed by a 6l-cm (2-
ft) length  of 3.2-mm (1/8-in.)  OD stainless steel tubing packed  with  60/80 mesh
Carbosieve  G.   The  Carbosieve  and  Unibeads columns must  be baked separately at
200°C with carrier gas flowing through them for 24 hours before initial use.
                         f
     2.3.4   Sample Injection System.   A 10-port  GC sample  injection valve  fitted
with  a sample loop properly sized to  interface  with  the NMO  analyzer   (1-cc loop
recommended).

     2.3.5  FID.  An  FID meeting the following  specifications is required:

     2.3.5-1   Linearity.   A linear response  (j+5  percent)  over  the operating range
as demonstrated by the procedures established in Section 5.2.3.

     2.3.5.2   Range.   A  full scale  range of  10  to  50,000 ppm  CHA.   Signal
                                                                                     o
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                                                               Section No.  3.17.10
                                                               Date May 31, 1991
                                                               Page 5

attenuators shall  be available to produce a minimum signal response  of  10 percent
of full scale.

     2.3.6    Data  Recording  System.    Analog  strip  chart   recorder  or  digital
integration  system compatible  with   the  FID  for  permanently  recording  the
analytical results.

     2.4  Other Analysis Apparatus.

     2.4.1  Barometer.   Mercury,  aneroid, or other barometer  capable of measuring
atmospheric pressure to within 1 mm Hg.

     2.4.2  Thermometer.  Capable of measuring the laboratory temperature to within
1°C.

     2.4.3  Vacuum Pump.   Capable of evacuating  to an absolute pressure  of 10 mm
Hg.

     2.4.4  Syringes.  10-ul and 50-ul liquid injection syringes.

     2.4.5  Liquid Sample  Injection  Unit.  316 SS U-tube  fitted with an injection
septum, see Figure 25~7-

3.  Reagents

     3.1 Sampling.  The following are required for sampling:

     3-1.1 Crushed Dry Ice.

     3-1.2  Coarse Quartz Wool.  8 to 15 urn.
          -  '   .•'
     3.1.3 Filters.  Glass fiber filters, without organic binder.

     3.2  NMO  Analysis.   The following gases  are needed:

     3.2.1 Carrier  Gases.   Zero grade helium (He) and oxygen  (02)  containing less
than 1 ppm C02 and less than 0.1 ppm C as hydrocarbon.

     3-2.2  Fuel Gas.  Zero grade hydrogen (H2), 99.999 percent pure.

     3.2.3  Combustion Gas.  Zero grade  air or 02  as required  by the detector.

     3-3  Condensate Analysis.   The following gases  are needed:

     3.3-1  Carrier Gas.  Zero grade air, containing less than 1 ppm C.

     3.3«2  Auxiliary 02.   Zero grade 02, containing less than 1 ppm C.

     3.3.3  Hexane. ACS grade,  for liquid injection.

     3.3.4  Decane.  ACS grade, for liquid injection.

     3.4  Calibration.  For all calibration gases, the manufacturer must recommend

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                                                               Section No.  3-17-10
                                                               Date May 31,  1991     -^
                                                               Page 6              (l

a  maximum  shelf  life for  each  cylinder  (i.e.,   the  length  of  time  the  gas
concentration is not  expected to change more  than  +_ 5 percent  from its certified
value).  The date of gas cylinder preparation,  certified organic concentration,  and
recommended maximum  shelf life  must  be affixed  to  each cylinder before shipment
from  the gas  manufacturer to  the buyer.   The following  calibration  gases  are
required:

     3.4.1   Oxidation  Catalyst Efficiency  Check Calibration Gas.   Gas  mixture
standard with nominal concentration of 1 percent methane in air.

     3.4.2  FID  Linearity and NMO Calibration Gases.   Three  gas mixture standards
with nominal propane concentrations of 20 ppm,  200 ppm, and 3000 ppm, in air.

     3.4.3  C02  Calibration Gases.   Three  gas mixture standards  with nominal  C02
concentrations of 50 ppm, 500 ppm, and 1 percent, in air.
     NOTE;  Total NMO of less than 1 ppm required for 1 percent mixture.

     3.4.4  NMO  Analyzer System Check  Calibration  Gases.  Four calibration gases
are needed as follows:

     3-4.4.1   Propane Mixture.   Gas  mixture standard  containing  (nominal)  50  ppm
CO, 50 ppm CH4, 2 percent C02, and 20 ppm C3H8, prepared in air.

     3.4.4.2  Hexane.   Gas mixture standard containing (nominal)  50 ppm hexane in s~*\

                                                                                   o
     3.4.4.3  Toluene.  Gas mixture standard containing (nominal) 20 ppm toluene in
air.
     3.4.4.4  Methanol.  Gas mixture standard containing (nominal) 100 ppm methanol
in air.

4.  Procedure

     4.1  Sampling.

     4.1.1  Cleaning Sampling  Equipment.   Before its  initial use  and  after each
subsequent  use,  a  condensate  trap  should  be  thoroughly cleaned and  checked to
insure that it is not contaminated.  Both cleaning and checking can be accomplished
by installing the  trap in the condensate recovery system and  treating it as if it
were a sample.   The trap should be heated  as  described in the  final  paragraph of
Section  4.3.3-   A trap may be  considered  clean when the C02  concentration in  its
effluent gas drops below  10 ppm.  This check is  optional for  traps  that have been
used to  collect  samples  which  were then recovered  according to  the  procedure in
Section 4.3.3.

     4.1.2  Sample Tank Evacuation and  Leak  Check.   Evacuate  the sample tank to 10
mm Hg absolute pressure or less.  Then close the sample  tank  valve, and allow the
tank to  sit for  60 minutes.   The tank is acceptable  if no change in tank vacuum is
noted.   The evacuation  and  leak check may  be conducted either in the laboratory or
the field.  The results of the leak check should be included in the test report.
     4.1.3  Sample  Train Assembly.   Just before assembly,  measure  the tank vacuum
using a  mercury U-tube manometer or absolute pressure gauge.   Record this vacuum,
                                                 V.
O

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                                                                Section No.  3.17.10
                                                                Date May 31,  1991
                                                                Page 7

 the  ambient temperature,  and  the barometric  pressure at  this time.   Close  the
 sample  tank valve  and  assemble the  sampling  system as  shown  in Figure  25~1.
 Immerse the condensate trap body in dry  ice.   The  point where the  inlet tube joins
 the trap body should be 2.5 to 5 cm above the top of the dry ice.

      4.1.4  Pretest  Leak Check.  A pretest  leak check is required.   Calculate or
 measure the approximate  volume of the  sampling train  from  the probe trip  to  the
 sample tank valve.   After assembling the  sampling train,  plug  the  probe  tip,  and
 make certain that  the sample tank valve is  closed.   Turn on  the  vacuum pump,  and
 evacuate the  sampling system  from  the  probe  tip  to the sample tank valve  to an
 absolute pressure of  10 ppm Hg or less.  Close the purge  valve,  turn off the pump,
 wait a minimum  period of 5 minutes,  and recheck the indicated  vacuum.   Calculate
 the maximum allowable pressure  change  based on a leak rate  of 1 percent  of  the
 sampling rate using Equation 25-1,  Section 6.2.  If the measured pressure change
 exceeds the calculated limit,  correct the problem before beginning sampling.   The
 results of the leak check should be included in the test report.

      4.1.5 Sample Train Operation.  Unplug the probe tip, and place the probe into
 the stack  such  that  the probe  is perpendicular to the duct  or  stack axis;  locate
 the probe  tip  at a single preselected  point of average velocity  facing away from
 the direction of gas  flow.  For stacks  having  a negative  static pressure,  seal the
El sample port sufficiently to prevent air in-leakage around the probe.  Set the probe
 temperature controller to  129°C (265°F) and the filter temperature  controller to
 121°C (250°F).   Allow the  probe and filter to heat  for  about 30  minutes  before
 purging the sample train.
      Close the sample valve, open the purge  valve,  and start the vacuum pump.  Set
 the flow rate between 60 and 100 cc/min, and purge the train with  stack gas for at
 least 10 minutes.  When  the temperatures at the exit ends of the  probe and filter
 are within their specified range, sampling may begin.
      Check  the  dry  ice  level around  the  condensate  trap,  and  add  dry ice  if
 necessary.   Record the  clock time.   To  begin  sampling, close the  purge valve  and
 stop the pump.   Open the sample valve  and the sample tank valve.   Using  the flow
 control  valve, set the  flow through the sample train to the  proper  rate.   Adjust
 the flow rate  as necessary to maintain a constant rate (+^10  percent) throughout the
 duration of  the sampling  period.    Record  the sample tank vacuum  and flowmeter
 setting  at  5~m±nute   intervals.   (See  Figure  25-8.)  Select  a  total sample  time
 greater  than  or equal to  the  minimum  sampling time  specified in  the  applicable
 subpart  of  the  regulation;  end  the sampling when this  time period  is  reached or
 when a constant  flow rate can no  longer  be maintained because of  reduced  sample
 tank vacuum.
      NOTE;   If  sampling had to be stopped  before obtaining  the  minimum  sampling
 time (specified in the applicable subpart) because a constant flow  rate could  not
 be maintained,  proceed as follows:  After closing the sample tank valve,  remove the
 used sample tank from the  sampling train  (without disconnecting other portions of
 the sampling train).   Take another evacuated and leak-checked sample tank,  measure
 and record the tank vacuum,  and attach  the new tank to the  sampling train.   After
 the new  tank is  attached to the sample train,  proceed with  the  sampling until  the
 required minimum sampling time  has  been  exceeded.

      4.2   Sample Recovery.   After  sampling is  completed,  close the  flow  control
 valve,  and  record the  final  tank  vacuum;  then  record the  tank  temperature  and
 barometric  pressure.   Close the sample  tank valve, and disconnect  the sample tank
 from the  sample  system.   Disconnect the  condensate  trap at the flowmetering system,

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                                                               Section No.  3.17.10
                                                               Date Hay 31,  1991
                                                               Page 8               S~\

and tightly seal both  ends  of the condensate trap.  Do not Include the  probe from
the stack to the filter as  part of  the  condensate  sample.   Keep the trap packed in
dry ice until the samples are returned to the laboratory for analysis.  Ensure that
the test run number is properly identified on the condensate trap and the
sample tank(s).

     4.3  Condensate Recovery.   See Figure  25-9.   Set the carrier  gas  flow rate,
and heat the catalyst to its operating temperature to condition the apparatus.

     4.3.1   Daily  Performance  Checks.   Each  day before  analyzing any  samples,
perform the following tests:
                            *. J
     4.3.1.1  Leak  Check,   With the carrier gas inlets and the flow control valve
closed, install a clean  condensate  trap in the system, and evacuate the system to
10 mm Hg  absolute pressure  or less.  Close the vacuum pump valve  and turn  off the
vacuum pump.  Monitor the system pressure for 10 minutes.   The system is acceptable
if the pressure change is less than 2 mm Hg.

     4.3.1.2  System Background Test.   Adjust  the  carrier  gas and auxiliary oxygen
flow rate to their  normal values  of 100 cc/min and  150  cc/min, respectively, with
the sample  recovery valve  in vent position.    Using a 10-ml syringe  withdraw a
sample from the system effluent through the syringe  port.   Inject this sample into
the NMO analyzer, and measure the C02 content.   The system background is acceptable
if the C02 concentration is less than 10 ppm.

     4.3.1.3  Oxidation  Catalyst  Efficiency Check.  Conduct  a catalyst efficiency \J
test as specified in  Section 5.1-2 of  this method.  If the  criterion of this test
cannot be met,  make the necessary repairs to the system before proceeding.

     4.3.2   Condensate  Trap  C02   Purge  and  Sample  Tank  Pressurization.    After
sampling  is completed,   the  condensate  trap  will  contain   condensed  water  and
organics and a small volume of  sampled  gas.  This gas from the stack may contain a
significant amount of C02 which must be removed from the condensate  trap before the
sample is recovered.  This  is accomplished by purging the condensate trap with zero
air and collecting the purged gas in the original sample tank.
     Begin  with the  sample  tank  and  condensate trap  from  the  test  run  to be
analyzed.   Set  the four-port  valve of  the condensate recovery system  in  the C02
purge position as shown  in  Figure  25-9-  With the sample tank valve closed, attach
the sample  tank  to  the sample recovery system.  With  the  sample recovery valve in
the vent position and  the flow  control  valve fully open,  evacuate the manometer or
pressure  gauge  to  the  vacuum of  the  sample  tank.    Next,  close  the  vacuum pump
valve, open the sample tank valve,  and  record the tank pressure.
     Attach  the  dry-ice-cooled   condensate  trap  to the   recovery system,  and
initiate  the  purge by  switching the  sample recovery valve  from vent  to  collect
position.   Adjust  the flow control valve to maintain atmospheric pressure in the
recovery  system.    Continue  the  purge  until  the  C02 concentration of the trap
effluent  is  less than 5  ppm.  C02 concentration in  the  trap effluent should be
measured by extracting syringe  samples from the recovery  system and analyzing the
samples with the NMO  analyzer.   This procedure should be  used only after the NDIR
response has reached a minimum level.  Using a 10-ml syringe,  extract a sample from
the syringe port prior to the NDIR, and inject this sample into the NMO analyzer.
o

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                                                               Section  No.  3.17.10
                                                               Date May 31, 1991
                                                               Page 9

      After the completion  of  the C02 purge,  use the carrier gas  bypass valve to
 pressurize the sample tank to approximately 1060 mm Hg absolute pressure with zero
 air.

      4.3.3 Recovery of the Condensate Trap Sample.   See Figure  25-10.  Attach the
 ICV to the  sample recovery system.   With; the  sample recovery valve  in a closed
 position,  between vent and collect,  and  the flow control  and ICV valves fully open,
 evacuate  the manometer or gauge,  the connecting  tubing,  and  the ICV  to 10 mm Hg
 absolute pressure.   Close  the flow-control and vacuum  pump valves.
      Begin auxiliary  oxygen flow  to  the oxidation  catalyst  at a  rate  of  150
 cc/min,  then  switch  the  four-way  valve  to  the trap  recovery position  and  the
 sample  recovery valve  to  collect position.   The system  should now be  set up to
 operate as indicated in Figure 25-10.  After the manometer or pressure gauge begins
 to  register a slight  positive pressure,  open the flow  control  valve.   Adjust the
 flow-control  valve  to  maintain  atmospheric  pressure  in  the   system  within  10
 percent.
      Now,  remove the  condensate  trap from the  dry ice,  and  allow it to  warm to
 ambient temperature while monitoring  the  NDIR response.  If after 5 minutes,  the
 C02  concentration of  the  catalyst effluent is  below 10,000 ppm,  discontinue the
 auxiliary  oxygen  flow  to the oxidation catalyst.  Begin heating the trap by placing
 it  in a furnace preheated  to 200°C.   Once heating has begun, carefully monitor the
 NDIR  response to ensure that  the catalyst effluent  concentration does not exceed
 50,000 ppm.   Whenever  the C02  concentration  exceeds  50,000 ppm,  supply auxiliary
 oxygen to  the catalyst at  the rate  of 150 cc/min.  Begin heating the tubing that
 connected  the  heated  sample box  to the  condensate  trap  only  after  the  C02
 concentration  falls  below  10,000 ppm.  This tubing may  be heated in the same oven
 as  the condensate  trap or with  an  auxiliary  heat  source  such  as  a  heat  gun.
 Heating temperature  must not exceed  200°C.   If a heat gun is used, heat the tubing
 slowly along its entire length  from the  upstream end to  the downstream end,  and
 repeat the pattern for a total of three times.   Continue  the recovery until the C02
 concentration  drops to  less than  10 ppm  as determined by syringe  injection as
 described under the  condensate trap C02 purge  procedure,  Section 4.3.2.
     After  the  sample recovery is completed,  use the carrier gas  bypass valve to
 pressurize the ICV to approximately 1060 mm Hg absolute pressure with zero air.

     4.4  Analysis.    Before putting the  NMO  analyzer  into   routine  operation,
 conduct an initial  performance  test.   Start the analyzer,  and perform  all  the
 necessary  functions  in order to put the analyzer into  proper working order;  then
 conduct the performance test  according to  the  procedures established  in Section
 5.2.  Once the performance  test has been successfully  completed and the C02 and NMO
 calibration response  factors have  been determined, proceed with sample analysis as
 follows:

     4.4.1 Daily  Operations and  Calibration Checks.   Before  and immediately after
 the analysis  of each set of samples or on a  daily basis {whichever occurs first),
 conduct a  calibration  test according to the procedures established in Section 5.3-
 If  the  criteria  of  the  daily  calibration  test cannot  be met,  repeat  the  NMO
 analyzer performance test  (Section 5*2) before proceeding.

     4.4.2 Operating Conditions.   The carrier gas flow  rate is  29.5 cc/min He and
2.2 cc/min 02 .   The column oven is  heated to 85°C.   The  order  of elutiori for the
sample from the column is CO, CHA, C02, and NMO.

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                                                               Section No.  3.17.10
                                                               Date May 31,  1991
                                                               Page 10

     4.4.3  Analysis  of Recovered  Condensate  Sample.   Purge  the sample  loop  with
sample, and then  inject  the  sample.   Under the specified operating conditions, the
CO, in the sample will elute in approximately 100 seconds.  As soon as the detector
response returns to baseline following the C02 peak, switch the carrier gas flow ,to
backflush,  and  raise  the column oven temperature to 195°C  as  rapidly as possible.
A  rate of  30°C/min has been shown  to be adequate.   Record the  value obtained for
the  condensible  organic  material  (Ccm)  measured  as C02  and  any  measured  NMO.
Return the  column oven temperature  to  85°C in preparation for  the next analysis.
Analyze each sample in triplicate, and report the average Ccm.

     4.4.4  Analysis of Sample  Tank.  Perform  the analysis  as  described in Section
4.4.3, but record only the value measured for NMO (Ctm).

     4.5 Audit  Samples.   Analyze a set of  two audit  samples  concurrently with any
compliance  samples  and  in  exactly  the  same manner  to  evaluate  the analyst's
technique and the instrument calibration.   The same analysts, analytical reagents,
and analytical  system shall be used  for the compliance  samples  and the EPA  audit
samples; if this  condition is met, auditing  of subsequent  compliance analyses for
the same  enforcement  agency within  30  days is not required.  An audit sample set
may  not  be used to  validate  different  sets of  compliance  samples  under the
jurisdiction of different enforcement agencies, unless prior arrangements are made
with both enforcement agencies.
     Calculate  the  concentrations of the audit samples  in  ppm using the specified
sample volume in  the  audit instructions.   (NOTE;   Indication of acceptable results
may be  obtained immediately by  reporting the  audit results  in  ppm and compliance
results in  ppm by  telephone to  the  responsible enforcement  agency.)  Include the
results of both audit samples, their  identification numbers, and the  analyst's name
with the results  of the compliance determination samples in appropriate reports to
the EPA  regional office  or the  appropriate  enforcement agency  during the 30-day
period.
     The  concentration of the  audit samples  obtained by the analyst shall  agree
within 20  percent of  the actual concentrations.   Failure  to meet the 20 percent
specification may require retests until the audit problems  are resolved.  However,
if the audit  results do  not affect the compliance or noncompliance status of the
affected facility,  the  Administrator may waive the reanalysis requirement, further
audits, or  retests and  accept  the results of the compliance test.  While steps are
being taken  to  resolve audit analysis  problems,  the  Administrator may also choose
to use the  data  to  determine  the  compliance or noncompliance  of  the affected
facility.                   .

5.  Calibration and Operational Checks

     Maintain a record of performance of each item.

     5-1 Initial Performance Check of Condensate Recovery Apparatus.  Perform  these
tests before  the system  is first placed  in operation, after  any  shutdown  of 6
months or more,  and after any major modification of the system, or  at the specified
frequency.

     5.1.1  Carrier  Gas and  Auxiliary 02 Blank Check.    Analyze each new  tank of
carrier gas or auxiliary 02  with the  NMO analyzer  to check  for contamination.
Treat the gas cylinders as noncondensible gas samples, and analyze according to the
procedure in Section  4.4.3.  Add together any  measured CHA, CO,  C02, or NMO.   The
                                                                                    o
o
o

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                                                               Section  No.  3.17.10
                                                               Date May 31, 1991
                                                               Page 11
 total  concentration must be less  than 5 ppm.
      5.1.2  Catalyst Efficiency Check.   With a clean  condensate  trap installed in
 the  recovery system,  replace the carrier gas  cylinder with the high level methane
 standard  gas cylinder  (Section  3 • **•!)•   Set  the four-port valve  to the recovery
 position, and attach an ICV  to the recovery  system.  With the sample recovery valve
 in  vent position  and the  flow-control and ICV valves  fully open,  evacuate the
 manometer  or gauge,  the  connecting  tubing,  and  the ICV  to 10  mm  Hg absolute
 pressure.  Close the flow-control and vacuum pump valves.
      After  the  NDIR response has stabilized, switch the sample recovery valve from
 vent  to collect.   When  the  manometer or pressure gauge begins to register a slight
 positive  pressure, open the flow-control  valve.   Keep the flow  adjusted so that
 atmospheric  pressure is  maintained  in  the  system within  10 percent.   Continue
 collecting the  sample in a normal manner until the ICV is filled to a nominal gauge
 pressure of  300 mm Hg.  Close  the ICV valve, and  remove  the  ICV from the system.
 Place the sample  recovery  valve  in  the  vent position,  and  return  the recovery
 system to its normal  carrier gas and normal operating conditions.  Analyze the ICV
 for  C02  using the  NMO analyzer;  the catalyst efficiency  is acceptable if the C02
 concentration is within 2 percent of  the methane  standard concentration.

      5.1.3  System  Performance  Check.   Construct  a  liquid sample  injection unit
 similar in  design  to  the unit  shown in Figure  25-7 •   Insert this  unit into the
 condensate recovery and conditioning system in place of a condensate trap, and set
 the carrier  gas and auxiliary 02 flow rates to normal operating levels.   Attach an
 evacuated ICV  to  the  system, and switch  from system vent to collect.   With the
 carrier gas  routed through  the injection unit and the oxidation catalyst, inject  a
 liquid sample  (See Sections 5.1-3«1  to 5-1-3-4)  into  the injection port.  Operate
 the  trap  recovery  system  as described  in  Section 4.'3«3«   Measure  the final ICV
 pressure, and then analyze the vessel  to determine  the C02  concentration.  For each
 injection, calculate the percent recovery using the equation in Section 6.6.
      The performance test is acceptable if the average percent  recovery is 100 +_ 10
 percent with a  relative standard deviation  (Section 6.9) of less than 5 percent for
 each  set of  triplicate injections as  follows:

      5.1.3.1  50 ul Hexane.

      5.1.3.2  10 ul Hexane.

      5.1.3.3  50 ul Decane.

      5.1.3.4  10 ul Decane.

      5.2 Initial  NMO Analyzer Performance Test.   Perform  these  tests before the
system is first placed  in operation, after  any shutdown  longer than 6 months, and
after any major modification of the system.

     5.2.1  Oxidation Catalyst   Efficiency  Check.   Turn   off  or  bypass the  NMO
analyzer reduction  catalyst.  Make triplicate injections  of the high level methane
standard (Section  3«^-l)-   The  oxidation  catalyst operation is  acceptable  if the
FID response is less than 1 percent of the injected methane  concentration.

     5.2.2  Reduction Catalyst   Efficiency   Check.    With  the  oxidation  catalyst
unheated or  bypassed  and the heated reduction catalyst bypassed,  make triplicate

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                                                               Section No.  3.17.
                                                               Date May 31 ,  1991
                                                               Page 12

injections  of  the  high  level  methane standard  (Section  3.4.1).    Repeat  this
procedure  with both  catalysts  operative.   The  reduction  catalyst  operation  is
acceptable if the response under both conditions agree within 5 percent.

     5.2.3 Analyzer Linearity  Check and NMO Calibration.   While operating both the
oxidation and reduction catalysts, conduct a linearity  check of the analyzer using
the propane  standards  specified in Section 3.4.2.   Make  triplicate  injections  of
each calibration gas,  and then calculate the average response  factor (area/ppm  C)
for each  gas, as well as the overall mean of the response  factor  values.   The
instrument  linearity  is acceptable  if  the  average response  factor  of  each
calibration gas is within 2.5 percent of the overall mean value and if the relative
standard deviation (Section 6.9) for each set of triplicate injections is less than
2 percent.   Record  the overall  mean  of the  propane response factor  values as the
NMO calibration response factor  (RFNMO).
     Repeat the linearity check using the C02  standards specified in Section 3-4.3-
Make triplicate  injections of  each  gas,  and then  calculate the  average response
factor  (area/ppm  C)  for  each gas,  as well as the overall mean of  the response
factor values.   Record the overall mean of  the response  factor values  as  the C02
calibration  response  factor   (RFV,-. ) .    Linearity is  acceptable  if the  average
response factor of  each calibratlbr? gas is within 2.5 percent  of the overall mean
value and if the  relative  standard deviation  for each set of triplicate injections
is less than 2 percent.  The RFC_  must be within 10 percent of the RFNM0.

     5.2.4  System  Performance Check.   Check  the column  separation and  overalllJ
performance  of the  analyzer   by  making triplicate  injections  of  the calibration
gases  listed in  Section  3-4.4.   The  analyzer performance  is acceptable  if the
measured NMO value  for each  gas  (average of  triplicate injections) is  within 5
percent of the expected value.

     5.3  NMO Analyzer Daily Calibration.

     5.3-1   C02 Response Factor.   Inject  triplicate  samples  of the high level C02
calibration  gas  (Section 3-4.3).   and calculate the average  response factor.  The
system operation  is adequate  if the calculated response factor is within 5 percent
of the RFpQ   calculated during the initial performance  test  (Section 5.2.3).  Use
the daily response  factor  (DFRCQ  ) for analyzer calibration and the calculation of
measured C02 concentrations in tKe ICV samples.

     5.3-2   NMO Response Factors.  Inject triplicate. samples of the mixed propane
calibration  cylinder  (Section 3-4.4.1),  and  calculate  the  average  NMO response
factor.   The  system operation is adequate  if  the  calculated  response  factor is
within  5 percent of  the  RFNMO  calculated  during  the  initial  performance test
(Section 5.2.4).   Use the daily  response  factor (DRFNMO) for analyzer calibration
and calculation of NMO concentrations in the sample tanks.

     5.4  Sample  Tank and ICV Volume.   The  volume of the  gas  sampling tanks used
must be determined.   Determine the tank and  ICV volumes by weighing them empty and
then filled  with  deionized distilled water;  weigh to the nearest  5  g,  and  record
the results.   Alternatively,  measure the volume of water used  to fill them  to
nearest 5 ml-

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                                                               Section  No.
                                                               Date May 31,
                                                               Page 13
 6.   Calculations
                                                                            3.17.10
                                                                            1991
     All equations  are written  using  absolute  pressure;  absolute  pressures are
determined by  adding the  measured barometric pressure  to the  measured gauge or
manometer pressure.

     6.1  Nomenclature.
            C   = TGNMO concentration of the effluent,  ppm C equivalent.
            Cc   = Calculated condensible organic  (condensate trap)  concentration
                  of the effluent,  ppm C equivalent.
            Ccm = Measured concentration {NMO analyzer)  for the condensate trap
                  ICV, ppm C02.
            Ct   = Calculated noncondensible organic concentration (sample tank)
                  of the effluent,  ppm C equivalent.
            Ctm = Measured concentration (NMO analyzer)  for the sample tank,
                  ppm NMO.
            F   = Sampling flow rate,  cc/min.
            L   = Volume of liquid  injected, ul.
            M   = Molecular weight  of the liquid  injected,  g/g-mole.
            mc   = TGNMO mass concentration of the effluent, mg C/dsm3.
            N   = Carbon number of  the liquid compound  injected (N =  12 for
                  decane,  N = 6 for hexane).
            Pf   = Final  pressure of the intermediate collection vessel, mm Hg
                  absolute.
            Pb   = Barometric pressure, cm Hg.
                  Gas sample tank pressure before sampling, mm Hg absolute.
                  Gas sample tank pressure after  sampling,  but before
                  pressurizing,  mm  Hg absolute.
                  Final  gas sample  tank pressure  after  pressurizing,  mm Hg
                  absolute.
                  Final  temperature of intermediate collection vessel, °K.
                  Sample tank temperature before  sampling,  °K.
                  Sample tank temperature at completion of sampling,  °K.
           Ttf  = Sample tank temperature after pressurizing,  °K.
             V = Sample tank volume,  m3.
             Vt  = Sample train volume, cc.
             Vv  = Intermediate collection vessel  volume,  m3.
             Vs  = Gas volume sampled,  dsm3.
             n  = Number of data  points.
             q  = Total  number of analyzer injections of  intermediate  collection
                  vessel during analysis  (where k = injection number,  1 ... q).
             r  = Total  number of analyzer injections of  sample tank during
                  analysis  (where j  =  injection number, 1 ... r).
             xx  = Individual measurements.
             x   = Mean  value.
             P   = Density  of liquid injected, g/cc.
             6   = Leak  check period,  min.
            AP   = Allowable pressure  change,  cm  Hg.
             • ti
             Pt
             t f
             ti
             T
     6.2  Allowable Pressure Change.
the allowable pressure change:
                                     For the pretest leak check, calculate

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                        AP = 0.01
                                                             Section No.  3.17.10
                                                             Date May 31. 1991
                                                             Page 14
                                                                     Eq. 25-1
     6.3  Sample  Volume.  For each test run,  calculate  the gas volume sampled:

                                                                     Eq. 25-2
                         v. = 0.3857 v
    t   _   * ti
                                             o
     6.4    Noncondensible  Organics.    For  each  sample  tank,  determine  the
concentration of nonmethane organics (ppm C):
                               t r
                               t f
                            P    P
                            rt   rt
                            T    T
                            1t   At
      i  E  ct
      r  3=1
                                                                      Eq. 25-3
     6.5  Condensible Organics.  For each condensate trap,  determine the concentra
tion of organics (ppm C):
                                                                       Eq. 25-4
                                           -O
               ;  Cc  =  0.3857
                            V*,
1   V    C
—   /-J
                                               cm,.
                                        k=l
     6.6 TGNMO.  To  determine  the  TGNMO  concentration  for  each test run, use the
following equation:
                          c  = ct + cc
                                  Eq. 25-5
     6.7  TGNMO Mass  Concentration.  To determine the TGNMO mass
concentration as carbon  for each test run, use the following  equation:

                        mc = 0.4993 C
                                  Eq. 25-6
     6.8 Percent  Recovery.    To calculate  the percent  recovery  for  the liquid
injections  to  the  condensate  recovery and conditioning  system  use  the following
equation:
                                     M   vv  rf  c/cm
             Percent  recovery = 1.604 —  	  	
                                         P   T    N
                                  Eq. 25-7
O

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                                                              Section  No. 3.17.10
                                                              Date May 31, 1991
                                                              Page 15
     6.9  Relative Standard Deviation.
                               100 /r(x1  - :

                                - »    n - 1
                                x
                 - x)2
RSD = 	"W	                          Eq. 25-8
7.  Bibliography

     1.   Salo,  Albert E., Samuel  Witz,  and Robert D.  MacPhee.   Determination of
Solvent  Vapor  Concentrations  by  Total  Combustion  Analysis:    A  Comparison  of
Infrared with Flame  lonization Detectors.  Paper No. 75~33-2.   (Presented at the
68th  Annual  Meeting  of  the  Air  Pollution  Control  Association.    Boston,
Massachusetts.  June 15-20,  1975.)  14 p.
     2.   Salo,  Albert E.,  William L. Oaks, and  Robert  D.  MacPhee.   Measuring the
Organic Carbon  Content  of Source Emissions for  Air Pollution Control.   Paper No.
74-190.    (Presented  at  the  67th  Annual Meeting  of  the Air  Pollution Control
Association.  Denver, Colorado.   June 9-13,  1974.) 25 p.

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                                                            Section  No.
                                                            Date May 31,
                                                            Page 16
                                                                            3.17.10
                                                                            1991
o
                                        REGULATING
                                           VALVE
                                                                        MANOMETER
                    DUAL RANGE
                    ROTAMETER
         TEMPERATURE
         CONTROLLER
                                                    VACUUM PUMP
THERMOCOUPLES
                         PURGE VALVE

                                THERMOCOUPLE
                                          ROTAMETER |    |
STACK
WALL
                                                                     SAMPLE
                                                                      TANK
                                                                      VALVE
                         SAMPLE
                         VALVE
                     STAINLESS STEEL
                     FILTER HOLDER
                  HEATED BOX
                                                      CONDENSATE
                                                         TRAP
           STAINLESS
          STEEL PROBE
O
                                                                             SAMPLE
                                                                              TANK
                           Figure 25-1. Sampling train.
                                                                                    O

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                                                                Section No.  3.17.10
                                                                Date  May 31,  1991
                                                                Page  17
                                   VACUUM PUMP
                                    CONNECTOR
                                                   SAMPLE
   25.4
    1.0
 F1BERFAX
INSULATION
         DIMENSIONS: HE1
                     in
                                                                                 3.175
                                                                                 0.125
                                                                             CONDENSATE
                                                                             TRAP PROBE
                                                                              BULKHEAD
                                                                              CONNECTOR
                                                                              J
PROBE
NNECTOR
           PROBE LINE
         THERMOCOUPLE
                            TO TEMPERATURE
                               CONTROLLER
                      a                    a
                   FILTER HEAT            CONDENSATE
                  TEMPERATURE            TRAP PROBE
                   CONTROLLER             CONNECTOR
                  THERMOCOUPLE         THERMOCOUPLE
                             Figure 25-2. Out-of-stack filter box.
                                                              . \ t_-

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                                                             Section No.
                                                             Date May 31,
                                                             Page 18
3.17.10
1991
                                                                       o
DIMENSIONS:
nrn
 in
                                                           0.375       0.035
                                                               316SS TUBING
                                                                    31 ess NUT
WALL
                                                                                   O
                                                            COARSE QUARTZ
                                                            WOOL PACKING
                                    2.25
                          Figure 25-3.  Condensate trap.
                                                                                   O

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eftf
                                                                       Section No.  3-17.10
                                                                       Date May 31.  1991
                                                                       Page 19
                            FLOW METERS
                                                          HEATTRACE(100°C)
                                                   SAMPLE
                                                 RECOVERY
                                                   VALVE
                                 FLOW
                               CONTROL
                                 VALVE
                                                                            SYRINGE PORT
              VACUUM PUMP
                                    Figure 25-4. Condensate recovery system.

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                                                  Section  No.  3.17.10
                                                  Date May 31, 1991    S~\
                                                  Page 20              (J
                           CARRIER GAS
CALIBRATION STANDARDS —1>
         SAMPLE TANK
                               i
 SAMPLE
INJECTION
  LOOP
    INTERMEDIATE COLLECTION
<3—  VESSEL (CONDmONED
          TRAP SAMPLE)
                           SEPARATION
                             COLUMN
                                        BACKFLUSH
            CO.CH4lC02
              NONMETHANE
                ORGANICS
                           OXIDATION
                            CATALYST
                           REDUCTION
                            CATALYST
                             FLAME
                           IONIZATION
                            DETECTOR
                HYDROGEN
               COMBUSTION
                   AR
                         DATA RECORDER
                                                                       o
   Figure 25-5. Simplified schematic of nonmelhane organic (NMO) analyzer.
                                           O
                                             , •)

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                                                            Section  No.  3.17-10
                                                            Date May  31,  1991
                                                            Page 21
                                          COLUMN OVEN
                                    rOQOOOOOOOOOOOQQQOOOQQQ
      REDUCTION
       CATALYST
H2  AIR
                    Figure 25-6.  Nonmethane organic (NMO) analyzer.

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      CONNECTING T
                       INJECTION
                       SEPTUM
                                                             Section  No.
                                                             Date May 31,
                                                             Page 22
                                                    CONNECTING ELBOW
3.17.10
1991
 FROM
CARRIER
DIMENSIONS:
       o
  .   TO
   CATALYST
                                                                                  O
                                                              31 eSS TUBING
                         Figure 25-7.  Liquid sample injection unit.
        O
                                                                                8/89

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                                                                 Section No.  3-17-10
                                                                 Date May 31, 1991
                                                                 Page 23
                                 VOLATILE ORGANIC CARBON
FACILITY
LOCATION
DATf
TAWXNUMBfn
SAMPLE IOCAT(OM
OPERATOR
OHM UllUf CO
TBAFWUMBEH «AU»1 f 10 MUMBFH
"V : TAWXVACUUU.
.: mm Hf cm Hf
PRETEST (MANOMETER)
POST TEST (MANOMETER)

ICAUCfJ
(RAUCri

• BAROMETRIC
PRESSURE.
mm Nf



AMBIENT
TIUPtRATURE,
•c



LEAK RATE
     cm H| / 10 min
                  PRETEST.
       TIME
   CLOCK/SAMPLE
VACUUM
 cm H|
flOWMETIR SITTING
                              COMMENTS
                     Figure  25-8.  Example field data form.

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                                                    Section No.  3.17.10
                                                    Date May 31,  1991
                                                    Page 2H
                                                   o
             FLOW METERS
                     AIR
                   HEAT TRACE (100'C)

                 n
                                              H2OTRAP
                                              4-PORT VALVE
                            CONDENSATEi
                               TRAP
                 FLOW
               CONTROL
                 VALVE
              C_DRYICE_^
                                  VENT
                                  SAMPLE
                                 RECOVERY
                                  VALVE
                                                NDIR
                                              ANALYZER
                                                             LJ^LJ u-**1—'n' ^ ^<
                                                              OXIDATION
                                                               REACTOR
                                    SYRINGE PORT
  C7
VACUUM PUMP
                            SAMPLE
                             TANK
                             VALVE
SAMPLE
 TANK
                                                                         O
                 Figure 25-9. Condensate recovery system, CO2 purge.
                                                    O

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                                                           Section  No.  3.17-10
                                                           Date May  31,  1991
                                                           Page 25
              FLOW METERS
                                             HEATTRACE(100°C)
                                     SAMPLE
                                    RECOVERY
                                      VALVE
                   FLOW
                 CONTROL
                   VALVE
SYRINGE PORT
VACUUM PUMP
             Figure 25-10.  Condensate recovery system, collection of trap organics.

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o
o
o

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                                                               Section  No.  3.17.11
                                                               Date May 31. 1991
                                                               Page 1


 11.0  REFERENCES

 1. Evaluation of Trap Recovery Design,  EMB Project Number 82SFS-1.

 2. Preparation  of  Method  25  Sampling Equipment  and  Determination  of  Linit of
    Detection of Quantification, EMB Project No.  82SFS-1.

 3. Evaluation of  Method 25  Condensate  Trap Packing Material,  EMB Project Number
    82SFS-1.

 4. Oxidation Catalyst Screening and Evaluation Study,  ESED Project  Number 82SFS1-4-
    2.

 5. Quality Control Procedures Evaluation,  ESED Project Number 82SFS1-4-3.

 6. Condensate Trap Development and Evaluation, ESED  Project Number  82SFS1-4-4.
    •\
 7. Trap Recovery Procedures Evaluation.  ESED Project Number 82SFS1-4-5.

 8. Evaluation of Particulate Filters,  ESED Project Number 82SFS1-5-2.

 9. "Procedure for  NBS-Traceable  Certification of Compressed Gas Working Standards
    Used for Calibration  and  Audit of  Continuous Source  Emission Monitors  (Revised
    Traceability Protocol No.  1)," June 1987, Section 3.0.4 of the Quality Assurance
    Handbook for Air Pollution Measurement  Systems,  Volume III, Stationary Source
    Specific Methods, EPA-600/4-77-027b,  August 1977.  U.  S. Environmental Protection
    Agency, Office of Research  and Development Publications,  26  West St. Clair  St.,
    Cincinnati, OH  ^5268.

10. "A Procedure for Establishing Traceability of Gas Mixtures  to  Certain  National
    Institute  for  Standards  and Technology  Standard Reference Materials," Joint
    Publication  by  NIST  and  EPA,  EPA-600/7-81-010,  Available  from U.  S.
    Environmental Protection  Agency,  Quality  Assurance  Division (MD-77).  Research
    Triangle Park,  North Carolina 27711.

11. R. S.  Wright,   C.  V.  Wall,  C.  E.  Decker,  and  D.  J.  von  Lehmden,  "Accuracy
    Assessment of  EPA  Protocol  Gases  in 1988,"  Journal  of  the  Air  and Waste
    Management Association.  29_ (9):  1225-1227,  September  1989.

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o
o
o

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                                                              Section No 3.19
                                                              Date September 3, 1992
                                                              Page 1
                                    Section 3.19
                METHOD 101A-DETERMINATION OF PARTICULATE AND GASEOUS
                      MERCURY EMISSIONS  FROM STATIONARY SOURCES
                                       OUTLINE
Section


SUMMARY


METHOD HIGHLIGHTS


METHOD DESCRIPTION


       1.     PROCUREMENT OF APPARATUS
              AND SUPPLIES


       2.     CALIBRATION OF APPARATUS


       3.     PRESAMPLING OPERATIONS


       4.     ON-SITE MEASUREMENTS


       5.     POSTSAMPLING OPERATIONS


       6.     CALCULATIONS


       7.     MAINTENANCE


       8.     AUDITING PROCEDURE


       9.     RECOMMENDED STANDARDS FOR
              ESTABLISHING TRACEABILITY


      10.     REFERENCE METHODS


      11.     REFERENCES
Documentation
3
3
3
3
3
3
3
3
3
3
3
3
3
.19
.19
.19
.19
.19
.19
.19
.19
.19
.19
.19
.19
.19


.1
.2
.3
.4
.5
.6
.1
.8
.9
.10
.11
Number
of Paaes
1
2
18
25
1
19
29
10
4
4
1
18
2

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o
o
o

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                                                               Section No 3.19
                                                               Date September 3,  1952
                                                               Page 1
                                       SUMMARY
         Method 101A, for determining particulate and gaseous mercury  (Hg) emissions
from stationary sources, is similar to Method  101.  In 101A,  however, acidic potassium
permanganate  (KMnO<) solution is used for sample collection instead of acidic  iodine
monochloride.  This method applies  to determining particulate and gaseous mercury (Kg)
emissions  from sewage  sludge incinerators and other  sources  as specified  in the
regulations.   Particulate and gaseous Hg emissions are withdrawn  isokinetically from
the source and collected in  an acidic KMnO4 solution.  The collected Hg (in mercuric
form)  is  reduced  to elemental Hg,  which  is then aerated from  the  solution into an
optical cell and measured by  atomic  absorption  spectrophotometry  (AAS).
         After initial dilution,  the range of this method is 20  to 800  ng Hg/mL. The
upper limit can be extended by further dilution  of the sample. The sensitivity  of the
method depends on the recorder/ spectrophotometer combination selected.  The collection
efficiency of the  sampling method can be affected by excessive oxidizable matter in the
stack-gas that prematurely depletes  the KMn04  solution.
         The method descriptions given are based on the method1'2'3  promulgated October
15,  1980,  and on  corrections and  additions  published  on  September  12,  1984, and
September 23,  1988  (Section 3.19.10).

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o
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o

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                                                               Section No 3.19
                                                               Date September 3,  1992
                                                               Page 1
                                  METHOD HIGHLIGHTS
          Section 3.19  describes  the procedures and  specifications  for determining
 particulate and gaseous mercury emissions from sewage sludge incinerators and other
 stationary sources as  specified  in  the regulations.   New  procedures  were added to
 Method 101A3 on the  basis of  EPA-conducted  development and evaluation  of mercury
 sampling  and analysis.   The major changes  for Method  101A are:
          1.    The impinger KMnO4  absorbing solution  and the 8  N hydrochloric acid
               (HCl)  rinse are no  longer combined in the field during sample recovery.
          2.    The impinger KMn04  absorbing solution must be  filtered.
          3.    The filtrate must be analyzed within 24 h of  filtration.
          4.    The residue on  the filter from the filtration step must be  digested .with
               8 N HCl.
          5.    The HCl digestate and  the final field sample  recovery rinse qf HCl are
               combined and analyzed separately  from the KMnO4 filtrate.     :;

 1.        Procurement  of' Apparatus  and Supplies                ;     ,,     .  •,,. -,.....

          Section 3.19.1  (Procurement of Apparatus and  Supplies) gives specifications,
 criteria, and design features  for the equipment find materials required for'Method 101A.
 This section can be used as a  guide for procuring and initially checking  equipment and
 supplies.  The activity  matrix (Table 1.1) at the end of the section is a summary of
 the details  given in  the text and  can be used as a quick reference.

 2.        Pretest Preparations

          Section 3.19.2  (Calibration of Apparatus)  describes the  required calibration
procedures  and considerations  for  the  Method  101A  sampling equipment.   Required
accuracies for each component also are included.  A pretest checklist (Figure  3.1 in
Subsection 3.19.3) or a  similar form should be used to summarize the calibration and
other pertinent pretest  data.  The calibration section may be removed along with the
corresponding sections for the other methods and made into a separate quality assurance
reference manual for personnel involved in calibration activities. :  -.
         Section 3.19.3  (Presampling Operations)  provides  testers with a guide for
preparing equipment and  supplies  for field tests.  A pretest preparation form  can be
used as an  equipment  checkout and packing list.   Because of the potential for high
blank  levels,  special attention must be  paid to preparing the sampling equipment.
Also,  testers must ensure that any required audit samples are obtained for  the test by
the responsible regulatory agency.
         Activity matrices for calibrating the  equipment and the presampling operations
 (Tables 2.1 and 3.1) summarize the activities.

3.       On-Site Measurements

         Section 3.19.4  (On-Site  Measurements)  contains step-by-step procedures for
sample collection,  sample recovery, and sample preparation for transport. The on-site
checklist  (Figure  4.3,   Section  3.19.4) provides  testers  with  a quick  method for
checking  the  on-site  requirements.  Table 4.1  provides an  activity matrix for all
on-site activities.                                                             c -

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                                                              Section No 3.19
                                                              Date September 3, 1992
                                                              Page 2
o
4.       Posttest Operations
         Section  3.19.5   (Posttest  Operations)  presents  the  posttest  equipment
procedures  and a  step-by-step analytical procedure  for determination  of  mercury, .
Posttest calibrations are required for the sampling equipment.  The posttest operations,
form  (Figure 5.9,  Section 3.19.5)  provides  some key  parameters  that  testers and
laboratory personnel must  check.  The step-by-step sample preparation ,and analytical
procedure  descriptions  can be  removed and made  into a  separate  quality  assurance
analytical1reference manual for laboratory personnel.
         Section 3.19.6  (Calculations) provides testers with the required equations,
nomenclature, and  significant  digits.   A calculator  or  computer should  be  used, if
available, to reduce the chances of error.
         Section 3.19.7  (Maintenance) provides testers with  a guide for a maintenance
program.  This program is  not required, but it should reduce equipment malfunctions.
Activity matrices (Tables 5.1,  6.1,  and 7.1) summarize all postsampling, calculation,
and maintenance activities.

5.       Auditing Procedures

         Section  3.19.8   (Auditing  Procedure)  provides  a description of  necessary
activities  for  conducting performance and  system  audits.     The  data-processing.*—^
procedures and  a  checklist for a  systems  audit also are included  in this  section/   j
Table 8.1 is an activity matrix for conducting the performance and system audits.   \^S
         Section 3.19.9 (Recommended Standards for Establishing Traceabi-lity) provides
the primary standard to which the analytical data should be traceable.

6.       References

         Section 3.19.10  contains the promulgated Method 101A; Section  3.19.11 contains
the references cited throughout the text.
                                                                                    O

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                                                               Section No.  3.19.1
                                                               Date September J,  1992
                                                               Page 1


 1.0      PROCUREMENT OP APPARATUS AND SUPPLIES

          Before  Method  101A can yield  results,  it  must  be  employed accurately.
 Consequently, all users are advised to read this document and to adopt its procedures.
 Alternative  procedures  should be  employed only if they are outlined  herein.
          This section describes  equipment specif ications/'briteria, and design features
 for the sampling train used for  Method  101A.   It  is intended to  help  users  with
 equipment.selection.  A schematic of  the  sampling train is shown in  Figure  1.1 as an
 aid in  the discussion that  follows.
         This  section also  describes  procedures  and  limits,  where applicable,  for
 acceptance  checks.   Calibration  data generated  by the acceptance  checks  should be
 recorded  in  the  calibration  log book.
         When procuring equipment and supplies,  users should record the descriptive
 title of  the equipment,  identification number  (if applicable), and the  results cf
 acceptance checks in  a  procurement log.                    .._  ,
         The following  procedures and descriptions are provided only as guidance and
 may not be  required for the initial ordering and  check-out of  the  equipment  ar.d
 supplies.  Testers should note,  however, that many of these procedures are required at
 a later step in the sampling and analytical procedures. Instituting  these or similar
 procedures as routine practices for checking new equipment and supplies,  therefore,
 will prevent later problems and/or delays  in  test programs.   At  the end of  this
 section, Table 1.1 provides a summary of quality assurance activities for procurement
 and acceptance of apparatus  and supplies.

 1.1      Sampling                            :

         The sampling train  shown in Figure 1.1  is  similar to the Method 5 train
 (Method 5 refers to 40 CFR Part 60).   The  Method 101A  sampling train consists of the
 following components:

 1.1.1    Nozzle—The  nozzle  shall be made  of nickel,  nickel-plated  stainless-steel,
quartz,  or borosilicate  glass.   The  tapered angle  should be <30°,  with taper on the
outside to preserve a constant  inside  diameter (ID).     • . . :.
         A range of  nozzle  ID's-for example, 0.3,2 to  1.27  cm (0.125 to 0.5  in.)-in
 increments of 0.16 cm (0.0625 in.) should be available for isokinetic sampling. Larger
nozzle sizes may be required if very  low  flows are encountered.
         Upon receipt of the nozzle(s) from the manufacturer,  users should  inspect it
 for roundness, for  the  proper  material, and for damage  to the tapered edge (nicks,
dents,  and burrs).  Check the diameter with a micrometer; calibration procedures are
described in Section 3.18.2.  A slight variation from exact  sizes  is normal.  Engrave
 each nozzle with an  identification number  for inventory and calibration purposes.  See
Section 3.18.3 for proper cleaning procedures.

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                         HEATED AREA
TEMPERATURE
   SENSOR

     PROBE
THERMOMETER
        \  FILTER HOLDER
         T	 (OPTIONAL)    THERMOMETER
                                                                       CHECK
                                                                       VALVE
       TYPE S
     PITOT TUBE
           PITOT MANOMETER
                                            IMPINGERS
                            THERMOMETERS
 TEMPERATURE SENSOR
                BY-PASS VALVE
                       f
                     PROBE
  CJ>
         	1	
      PITOT TUBE
                            ICE BATH
                               MAIN
VALVE
 /
                                VACUUM
                                GAUGE
                                                                            »o o w
                                                                            DI p> ro
                                                                            (Q rr o
                                                                            (0 0> rr
                                                                            KJ tn o
                                    VACUUM   »z
                                             (0 o
                            DRY G
                            METER
                         AIR TIGHT
                          PUMP
       LINE
               U)
               .
               to
  o
                   Figure 1.1.  Schematic of Met]wd 101A sampling train.
                                             10
                                             U3
                                             to
                                            O

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                                                               Section  No.  3.19.1
                                                               Date September 3,  1992
                                                               Page 3

  .1.2    Pi tot  Tube-The pitot tube,  preferably of Type  S design,  should meet the
requirements of Method 2, Section 3.1.2 of this Handbook.   The  pitot tube is attached
to  the  probe  as  shown  in  Figure  1.1.    The  proper  pitot-tube/sampling-nozzle
configuration to prevent aerodynamic interference is shown in  figures 2.6 and 2.7 of
Method 2, Section 3.1.2 of this Handbook.
         The pitot tube should be inspected visually for both vertical and horizontal
tip alignments.   If the tube is purchased as  an  integral  part of a  probe assembly,
check  the  dimensional clearances using  figures 2.6 and  2.7   (of Method  2,  Section
3.1.2).   Repair or  return any pitot tube that does  not meet specifications.   The
calibration procedure for a pitot tube is covered in Section 3.4.2 of this Handbook.

1.1.3    Differential Pressure AP-The differential pressure gauge should be an inclined
manometer or the equivalent,  as specified in Method 2,  Section 3.1.2 of this Handbook.
Two gauges are required.  One is  used to monitor the stack velocity pressure, whereas
the other is used to measure the orifice pressure differential.
         Initially, check the gauge against a gauge-oil manometer at a minimum of three
points:  0.64 mm (0.025 in.);  12.7 mm (0.5  in.); and 25.4 mm (1.0 in.) H20.  The gauge
should read within 5% of the gauge-oil manometer at each test point.  Repair or return
to the supplier any gauge that does not meet these  requirements.

1.1.4    Probe Liner—The probe liner is made of borosilicate or quartz  glass tubing.
(Note: Do not use metal  probe  liners.)   If a filter is used ahead of the impingers,
testers must use the probe heating system to  minimize the condensation of gaseous Hg.
A heating system is required  that will maintain an exit gas temperature  of 120 ± 14 °C
k(248 ± 25 °F) during sampling.  Other temperatures may be specified by a  subpart of the
 egulations and must be  approved by the  Administrator for a particular application.
 ecause the actual probe outlet temperature is not usually monitored during sampling,
probes constructed in accordance to APTD-0581 and calibrated according  to procedures
in APTD-0576 will be acceptable.
         Either borosilicate or quartz glass  liners may be used  for stack temperatures
up to about 480 °C  (900 °F),  but quartz glass liners must be used from 480 to 900 °C
(900 to 1650 °F).  Either type of liner may be used at higher  temperatures for short
periods,  with Administrator approval.  However,  the absolute upper limits—the softening
temperatures of 820  °C  (1508  °F) and 1500 °C (2732 °F)-for borosilicate and quartz,
respectively, must be observed.
         Upon receiving a new probe, users should  check it  visually to see whether it
is the length and composition ordered.  The probe  also  should be checked visually for
breaks or cracks,  and it should be checked for leaks on a sampling  train  (Figure 1.1).
Leak checks should  include a proper nozzle-to-probe connection with a  Viton O-ring,
Teflon® ferrules, or asbestos string.
         The probe heating system should be checked as follows:
         1.   With  a nozzle attached,  connect the  probe  outlet to  the inlet of the
              metering  system.
         2.   Connect  the probe  heater to an outlet and  turn  it  on  for 2 or 3 min.
              The probe should become warm to the touch.
         3.   Start  the pump and adjust the  needle valve  until it  indicates a  flow
              rate  of about  0.02 mVmin  (0.75  ftVmin) .
         4.   Be  sure  the probe remains  warm to  the  touch;   the heater  should be
              capable  of maintaining  an  exit  air temperature of  100 °C  (212 ^F)
              minimum.  Failure indicates that the probe should be repaired,  returned
              to  the supplier, or rejected.

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                                                               Section  No.  3.19.1
                                                               Date September 3,  1992
                                                               Page 4

 1.1.5     Filter Holder (Optional;-The filter holders should be made of borosilicate
 glass with a rigid, stainless-steel wire-screen filter support.  Do not  use  glass  frit
 supports.  A silicone  rubber or Teflon gasket is essential  to provide a positive  seal
 against  leakage from outside or around the filter.  Upon receipt, assemble  the filter
 holder with a filter and conduct a leak check.   There should be no leak  at a vacuum of
 15  in. of Hg.

 1.1.6     Impingers-Four Greenburg-Smith impingers must be  connected in series  with
 leak-free, ground  glass fittings or any similar leak-free, noncontaminating fittings.
 For the first,  third,  and  fourth impingers, testers may use impingers that are modified
 by  replacing the tip with a 13-mm ID (0.5 in.) glass tube extending to 13 mm (0.5  in.)
 from  the bottom  of  the  flask.    The  connecting  fittings should form   leak-free,
 vacuum-tight seals.   See  Section 3.19.3  for  proper  cleaning procedures.
          Upon receipt  of  a standard Greenburg-Smith impinger, users  should fill the
 inner tube with water.  If the water does not drain  through the orifice  in  6 to 8  s or
 less, the impinger tip should be replaced or  enlarged to prevent an  excessive pressure
 drop  in  the sampling  system.  Each impinger should be  checked visually for damage:
.breaks,  cracks,  or manufacturing flaws,  such as poorly  shaped connections.

 1.1.7     Acid Trap-The acid  trap should  be a Min~e Safety Appliances™ airline filter,
 catalog  number  81857,  with acid  absorbing cartridge and suitable connections, or the
 equivalent.  Upon  receipt, check the part number  to ensure the part is correct.

 1.1.8     Filter Heating System-Any  heating  system may be  used that  is  capable of
 maintaining  the filter holder at 120 ±  14 °C  (248  ±  25 °F) during sampling.  Other
 temperatures may  be specified by a  subpart- of the regulations or approved by the
 Administrator for  a particular application.   A gauge capable of measuring temperatures
 to within 3 °C  (5.4 °F)  should  be provided to  monitor the temperature around  the filter
 during sampling.
          Before sampling,  the heating system  and the  temperature monitoring device
 should be checked.  For convenience, the heating element should be  easily replaceable
 should a malfunction occur during sampling.

 1.1.9    Metering  System-The metering system  should  consist of a vacuum gauge,  a vacuum
 pump, thermometers capable of  measuring  ±3  °C  (5.4 °F)  of  true value in the  range of
 0 to 90  °C  (32  to  194  °F) , a dry-gas meter with 2%  accuracy at  the required  sampling
 rate,  and related equipment  as shown  in  Figure  1.1.   Other systems  capable of
 maintaining  metering  rates  within  10% of  the  isokinetic  sampling  rate  and of
 determining sample volumes to within 2% of the  isokinetic rate may be used if  approved
 by  the Administrator.  Sampling  trains  with metering systems designed for  sampling
 rates higher than  those described in APTD-0581 and APTD-0576 may be used if the above
 specifications  can be met.  When the metering system  is used with a pitot  tube, it
 should  permit  verification  of  an   isokinetic  sampling rate  through  the use   of  a
 nomograph or by calculation.
          Upon receipt  or  after construction  of the  system,  users should perform  both
 positive  and negative pressure  leak checks  before beginning the  system calibration
 procedure described in Subsection 2.1 of Section 3.19.2.  Any leakage requires repair
 or  replacement  of  the  malfunctioning item.
                                                                                 i
 1.1.10    Barometer—A   mercury,  aneroid,  or   other  barometer  capable   of  measuring
 atmospheric pressure  to within ± 2.5 mm (0.1 in.)  Hg  is required.
          A  preliminary  check  of  a   new  barometer  should  be  made   against   a
 mercury-in-glass  barometer or the  equivalent.   In lieu of  a  barometer   check,  the
o
o
 o

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                                                               Section No.  3.19.1
                                                               Date September 3,  1992
                                                               Page 5

 absolute barometric pressure may be obtained from .a nearby weather service station and
 adjusted for elevation difference between the station and the sampling point.   Either
 subtract 2.5 mm Hg/30 m (0.1 in. Hg/100 ft) from the station value  for  an  elevation
 increase, or add  the same for an  elevation decrease.    If  the barometer   cannot be
 adjusted to within 2.5 mm {0.1 in.)  Hg of the reference barometric pressure,  it should
 be returned to  the manufacturer or  rejected.

 1.1.11   Gas Density Determination Equipment—& temperature sensor and a pressure gauge
 are required as described in Method 2 (Section 3.1.2 of this Handbook). Additionally,
 a gas analyzer as described by Method 3 may be required.  The temperature sensor should
 be permanently  attached  to  either the probe  or the pitot tube.  In either case, it is
 recommended that a fixed configuration (Figure 1.1) be maintained.  The sensor also may
 be attached just prior  to  field use,  as described in  Section 3.19.2.

 1.2      Sample Recovery

 1.2.1     Glass  Sample Bottles Sample  bottles should be 1000- and 100-mL without leaks
 and with Teflon-lined caps.  Upon  receipt,  check visually for cracks in the glass.
 Ensure  that the cap liners are Teflon, because  other material can result  in sample
 contamination and  reaction  with the KMnO«.   Beca~use of the potential  reaction of  the
    04 with  the  acid,  there may  be  pressure buildup  in  the sample storage bottles.
  enting  is  highly recommended.  A  No. 70-72 hole drilled  in the container  cap  and
 Teflon  liner has been found to  allow adequate venting without  loss of sample.

 1.2.2     Graduated Cylinder—A 250-mL cylinder is required.

 1.2.3     Funnel and Rubber Policeman—These items  are used to aid in transferring silica
 gel  to containers; they  are not necessary if silica gel  is weighed in the field.

 1.2.4     Funnel—A glass  funnel  is needed to  aid  in sample  recovery.

 1.3       Sample Preparation and Hg  Analysis

 1.3.1     Volumetric  Pipets-Class A  1-,  2-,  3-,  4-,  5-,  10-,  and  20-mL pipets  are
 required.

 1.3.2     Graduated Cylinder—A 25-mL cylinder is  required.

 1.3.3     Steam Bath-Refers  to 40 CFR,  Part  60, Appendix  B, Method  101A.

 1.3.4     Atomic Absorption  Spectrophotometer—Any atomic  absorption unit  is  suitable,
provided  it  has an open  sample presentation  area in which to mount the optical cell.
Follow the instrument settings recommended by the manufacturer.  Instruments designed
 specifically  for measuring mercury  using the  cold-vapor technique are  commercially
available and may be substituted for the atomic  absorption  spectrophotometer.

 1.3.5     Optical Cell—The optical cell should be  of cylindrical shape, with  quartz end
windows  and  having   the dimensions  shown  in  Figure  1.2.   Wind  the  cell  with
approximately  2 m of 24-gauge  nichrome  heating wire,  and  wrap  with  fiberglass
 insulation tape or the equivalent;  do not let the wires touch each other.  A heat  lamp
mounted above the cell or a moisture trap installed upstream of the  cell may be  used
as alternatives.  Upon receipt,  check the dimensions and the capability of the heating
system.

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                                                             Section No.  3.19.1
                                                             Date September 3,  195
                                                             Page 6
o
1.3.6    Aeration Cell—The  aeration  cell  should  be constructed  according  to  the
specifications in Figure  1.3.   Do  not use a glass frit as a substitute  for the  blowr.
glass bubbler tip shown in Figure  1.3.

1.3.7    Recorder--The recorder  must be matched to the output of the spectrophotometer
described above.   As  an alternative, an integrator may be used to determine peak area
or peak height.

1.3.8    Variable Transformer-This item is needed to vary the voltage on  the  optical
cell from 0 to 40 volts.

1.3.9    Hood-A hood i's-) required for venting the optical cell exhaust.

1.3.10   Flow Metering Valve-Refers to 40 CFR,.. Part 60,  Appendix B,  Method 101A.

1.3.11   Flow Meter—A  rotameter,  or  equivalent,  is required  that is  capable  cf
measuring a gas flow of 1.5 L/min.  Upon receipt, calibrate the flow meter at a flow
rate of 1.5 L/min with a  bubble meter or wet-test meter.

1.3.12   Aeration Gas Cylinder-The cylinder mustncontain nitrogen or dry,  Hg-free air
and must be equipped with a single-stage regulator.
                                                                                  O
                                                                                -o

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                                                       Section No.  3.19.1
                                                       Date  September 3,  1992
                                                       Page  7
                                    18/9 FEMALE BALL SOCKET
                LENGTH NECESSARY TO FIT SOLUTION CELL
                     TO SPECTROPHOTOMETER
                         (END VIEW)
                                             TO VARIABLE TRANSFORMER
   VENT TO HOOD
       4
9-mm 00
                                 9-mm OD  ,•£*&  2JS em
                                                  3.81 em DIAMETER
                                                  QUARTZ WINDOWS
                                                  AT EACH END
                     (FRONT VIEW)
   NOTES:
   CELL WOUND WITH 24-GAUGE NICHROME WIRE
   TOLERANCES ± 5 PERCENT
                 Figure  1.2.   Optical cell.

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                                                      Section No.  3.19.1
                                                      Date September 3,  1992
                                                      Page 8
                                                                                  o
                     FROM TANK

                 1	/"T"V 1B/B MALE BALL JOINT
                      T(r—7T          	4-mmDORE TEFLON STOPCOCK
                  I     IT   innnnien  _/  "^^
10/72 GROUND
10/22 GROUND
 CLASS JOINT
WITH STOPPER
                                                     TO
                                                     OPTICAL CELL
                                            18/8 MALE OALL JOINT
                                      ALL DIMENSIONS IN em
                                     UNLESS OTHERWISE NOTED
         BLOWN GLASS BUMUIR    COTTU POBT\ON
          AH-ROX. &0 by 1.0 em    4.0-«m OD by 3.C-cm ID
O
                                                                                    o
                   Figure  1.3.   Aeration  cell.

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                                                              Section No.  3.19 .1
                                                              Date September 3,  1992
                                                              Page 9

1.3.13   TuJbing-The tubing is required for connections.  Use glass tubing  (ungreased
ball and socket connections are recommended)  for all connections between the solution
cell and the optical cell;  do not use Tygon tubing, other types of flexible tubing, or
metal tubing as substitutes.  Testers may use Teflon,  steel, or copper tubing between
the nitrogen tank and the flow meter valve (Section 5.3.7), and Tygon, gum, or rubber
tubing between the flow meter valve and the aeration cell.

1.3.14   Flow Rate Calibration Equipment—This equipment consists of a bubble flow meter
or a wet-test meter for measuring a gas flow rate of 1.5 ± 0.1 L/min.

1.3.15   Volumetric Flasks—These flasks must be Class A, with pennyhead standard taper
stoppers; the required sizes are 100-, 250-,  500-, and 1000-mL.

1.3.16   Volumetric Pipets—These pipets must be Class A; the required sizes  are 1-, 2-,
3-, 4-, and 5-mL.

1.3.17   Graduated Cylinder- A 50-mL cylinder is required.

1.3.18   Magnetic Starrer— A general purpose laboratory-type stirrer  is required.
                                               -i
1.3.19   .Magnetic Stirring Bar— A Teflon-coated stirring bar is  required.

1.3.20   Trip Balance— A trip balance capable of weighing to ± 0.5 g  is required.  Upon
receipt, check balance with standard weights.

1.3.21   Analytical Balance-An analytical balance capable of weighing up to ± 0.5 me
is required.  Upon receipt, check balance with standard weights.

1.4      Alternative Analytical Apparatus

         If any  alternative analytical apparatus is   to be  used,  it must  pass the
performance  criteria  described  in  Section   3.19.5.5.   Alternative Hg  cold-vapor
analytical systems are available commercially  from most atomic absorption manufacturers
and employ  automated flow-injection techniques.   Such systems  automatically inject
sample  solutions  into continuous  reagent streams containing the  reducing reagent.
Mercury is usually measured as a solution concentration  (e.g.,  mg Hg/L).  An example
of a typical  cold-vapor AA instrument using  flow injection  is  shown in Figure  1.4.
Such systems are allowable as long as they meet the following criteria:

1.4.1    Calibration Curve Linearity—The system  must  generate  a linear calibration
curve,  and  two  consecutive samples of the same  aliquot  size and concentration  must
agree within 3% of their average.

-------
oooo
oooo
oooo
oooo
Autosampler
                       Multichannel Pump
            Inert Gas
            Dilute HC1
            Sample
                    H2S04
            Reducing Reagent
                                                     Mixing Colls
                                     Spectrophotometer w/ Optical Cell
                                                 Gas/Liquid Separator
                          To Vent
                                To Waste
            Figure 1.4.  Typical cold Vapor AA instrumentation using flow injection.

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                                                                            •o O  0
                                                                            o-O P
                                                                             U) U)
                                                                             vo
                                                                             to
                                                                       o

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                                                               Section No. 3.19.1
                                                         '-   •   Date September 3, 1992
                                                        '•'      Page 11

 1.4.2    Spike flecovery-The system must  allow  for recovery of a minimum of 95% of the
 spike when an aliquot of a source  sample is spiked with a known  concentration of Hg
 (II)  compound.

 1.5      Reagents

 1.5.1    Sampling  and  Sample  .Recovery-Use   ACS   reagent-grade   chemicals   or  the
 equivalent,  unless otherwise specified.   The  following  reagents are used in  sampling
 and recovery:      -----

          Water—Deionized distilled, , meeting ^ASTM specifications  for  Type I  Reagent
 Water—ASTM Test Method D 1193-77.  If high concentrations'of organic matter  are not
 expected  to be  present,  users may eliminate  the KMnO<  test  for oxidizable  organic
 matter.   Use this water  in  all dilutions and solution preparations.

          Nitric Acid (HNO3), 50% (v/v)-Mix-equal volumes of concentrated HNO3 and water,
 being careful to add the acid to  the water  slowly.

          Silica Gel—Indicating type, 6- to 16-mesh.  If previously used,  dry at 175 °C
 (350  °F)  for 2  h.   Testers  may use new silica  gel .as received.

          Filter (Optional)—Glass  fiber filter, without  organic binder,  exhibiting at
 least  99.95% efficiency on 0.3-Hm dioctyl phthalate  smoke particles.   Testers may use
 the filter in cases  where  the gas stream  contains  large  quantities  of  particulate
 matter, but  they  should  analyze blank  filters  for Hg content.

          Sulfuric Acid (H2SO4), 10%  (v/v;-Slowly add  100 mL of concentrated H2SO< to 500
 mL of water  and mix cautiously.

          Absorbing Solution, 4% KMnO, (w/v)— Prepare fresh daily.  Dissolve 40 g  of KMn04
 in sufficient 10% H2SO4 to make 1  L.   Prepare  and store in glass bottles  to  prevent
 degradation.

 Caution:  To  prevent  autocatalytic  decomposition of  the  permanganate solution, filter
 it through Whatman" 541 filter paper.   In addition,  owing to the reaction of the KKnO,
with  the  acid,  there may be  pressure  buildup in the sample  storage  bottle.   These
 bottles should not be filled to capacity and should  be vented,  both to relieve excess
pressure  and to  prevent  explosion of  the container: A No. 70-72 hole drilled in the
 container cap and Teflon  liner is  recommended.

          Hydrochloric Acid-Trace metals grade  HC1 is recommended.  If other grades sre
used,  the Hg level  must  be  less than 3 ng/mL Hg.  Upon  receipt, check manufacturer's
 guarantee or analyze  the  acid for  background contamination.

          Hydrochloric Acid,  8 AHDilute 67 mL of concentrated HC1  to 100  mL with water
 (slowly add  the HC1  to the water).

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                                                               Section No.  3.19.1
                                                               Date September  3,  1992
                                                               Page 12

1.5.2    Analysis—The reagents needed for analysis are listed below:

         Tin  (II) Solution—Prepare  fresh daily and keep sealed when  not being used.
Completely dissolve 20 g of tin  (II) chloride  [or 25 g of tin  (II) sulfate] crystals
(Baker™ Analyzed reagent grade or any other brand that  will  give a clear solution) in
25 mL of concentrated HC1.  Dilute to 250 mL with water.  Do not substitute  HN03, H2SO4,
or other strong acids for the HC1.

         Sodium Chloride-tfydroxyl&mine Solution-Dissolve 12 g of sodium chloride and
12 g of hydroxylamine sulfate  (or 12 g of hydroxylamine hydrochloride)  in water and
dilute to 100 mL.

         Hydrochloric Acid, 8 AMDilute 67 mL of concentrated HC1 to 100 mL with water
(slowly add the HCl to the water).

         Nitric Acid, 15% (v/v)— Dilute 15 mL of concentrated  HN03 to 100 mL  with water.

         Mercury Stock Solution,  1 mg Hg/mL-Prepare'and  store all Hg standard solutions
in borosilicate glass containers. Completely dissolve 0.1354 g of  Hg  (II)  chloride in
75 mL of water.  Add  10 mL of concentrated  HN03-~and adjust the volume to  exactly 100
mL with water.  Mix thoroughly.  This solution  is stable for at least 1 month.

         Intermediate Hg Standard Solution, 10 ug/mL—Prepare fresh weekly. Pipet 5.0
mL of the Hg stock solution  (Section 6.2.5)  into a 500-mL volumetric flask, and add 20
mL of 15% HNO, solution.  Adjust  the volume  to  exactly  500 mL with water.  Thoroughly
mix the solution.

         Working Hg Standard Solution,  200 ng Jfg/mL—Prepare fresh daily.  Pipet 5.0 mL
from the Intermediate Hg Standard Solution (Section 6.2.6)  into a 250-mL volumetric
flask.  Add 5 mL of 4% KMnO< absorbing solution  and 5 mL of 15% HNOj. Adjust the volume
to exactly 250 mL with water.  Mix  thoroughly.

         Potassium Permanganate,  5*  (w/v)—Dissolve 5 g  of KMn04 in water  and dilute to
100 mL.

         Filter-Use a Whatman 40, or equivalent.
o
o
                                                                                      o

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                                                               Section No.  3.19.1
                                                               Date September 3,  1992
                                                               Page 13
         TABLE 1.1  ACTIVITY MATRIX FOR PROCUREMENT OF APPARATUS AND SUPPLIES
 Apparatus
 |Acceptance  limits
I Frequency & method
I of measurement
I Action  if
 requirements
 are  not met
 Sampling


 Probe liner
         V  ,
 I
 (specified material
 |of construction;
 |equipped with
 (heating system
 |capable of
 (maintaining 120 °C
 |± 14°C  (248 °C ±
 125 °F) at the exit
1
(Visually check and
(run the  heating
(system
I
 Repair,
 return to
 supplier,  or
 reject
 Probe
 nozzle
 (Nickel, nickel-
 |plated stainless-
 |steel, quartz, or
 (borosilicate
 (glass, tapered <
 (30°; difference in
 (measured diameter
 |< 0.1 mm (0.004
 I in.); no nicks,
 (dents, or
 (corrosion
 I(Subsec. 1.1.2)
 I	____
(Visually  check
(before  each test;
(use a micrometer to
(measure ID before
|field use;  after
|each repair
I
I
 Reshape  and
 sharpen,
 return to"
 the  supplier,
 or reject
Pi tot tube
(Type S  (Sec.
 3.1.2); attached
 to probe with im-
 pact (high press-
 ure) opening plane
 even with or above
 nozzle entry plane
(Visually  check for.
(both vertical  and
(horizontal  tip
(alignments;
(calibrated  according
 to Sec. 3.4.2
 Repair  or
 return  to
 supplier
Differ-
ential  *
pressure
gauge
 Meets criteria
 (Sec. 3.1.2);
 agree, within 5%
 of gauge-oil
 manometer
(Check against a
(gauge-oil  manometer
(at a minimum of 3
(points;  0.64
I(0.025); 12.7 (0.5);
(25.4 (1.0)  ram (in)
JH20
I	
 Repair or
 return to
 supplier
Vacuum
gauge
 0-760 mm (0-30
 in.) Hg, ± 25 mm
((1 in.)  at 380 mm
(in.) Hg
|Check against
(mercury  U-tube
(manometer  upon
|receipt
 Adjust or
 return to
 supplier
(Continued)

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                                                               Section No.  3 .19.1
                                                               Date September 3.  1992 S~*\
                                                               Page 14               (    )
TABLE 1.1   (Continued)
Apparatus
Vacuum pump
Orifice
meter
Impingers
Filter
holder
(optional)
Filter
support
Filter
heating
system
Dry-gas
meter
|
1
(Acceptance limits
1
(Leak free; capable
|of maintaining a
| flow rate of
JO. 02 - 0.03 mVmin
j (0._66 to 1.1
(ftVmin) for pump
| inlet vacuum of
380 mm (15 in.) Hg
1
|AH@ of 46.74 ±
J6.35 mm (1.84 ±
J0.25 in.) H20 at
J68 °F (not
(mandatory)
Four Greenburg-
| Smith connected in
|a series, leak-
|free, noncontamin-
ating fittings
Leak-free;
jborosilicate glass
1
(Rigid stainless-
| steel wire screen
| Capable of
(maintaining filter
(holder at
temperature of
120 °C ± 14 °C
(248 °F ± 25°F)
Capable of
measuring volume
within 2% at a
flow rate of
0.02 mVmin
(0.75 ftVmin)
Frequency & method
of measurement
Check upon receipt
for leaks and
capacity
Upon receipt,
visually check for
damage and calibrate
against wet-test
meter .-,—
'. -
Visually check upon
receipt; check
pressure drop
(Subsec. 1.1.6)
Visually check
before use; conduct
leak check
Visually check upon
receipt, conduct
leak check
Visually check upon
receipt and run
heating system
checkout
Check for damage
upon receipt and
calibrate (Sec.
3.4.2) against
wet-test meter
Action if
requirements
are not met
Repair or
return to
supplier
Repair, if
possible,
otherwise
return to
supplier
Return to
supplier
As above
Repair or
return to
manufacturer
1
| Repair or
return to
| manufacturer
1
1
(Reject if
(damaged,
(behaves
erratically,
| or cannot be
(properly
adjusted t i
                                                                                     o
                                                                                     o
(Continued)

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 TABLE 1.1  (Continued)
                                                               Section No. 3.19.1
                                                               Date September 3,  1992
                                                               Page 15
 Apparatus
(Acceptance limits
Frequency & method
of measurement
(Action if
 requirements
 are  not met
 Acid Trap
(Mine Safety Appli-
|,ances air line
[filter acid ab-
|sorbing cartridge
Visually check upon
receipt
 Return  to
 supplier
Thermo-
meters
|± 1 °C (2 °F)  of
|true value in the
|range of 0 to
J25 °C (32 to
|77 °F) for impin-
|ger thermometer
land ± 3 °C
1(5.4 °F)  of true
lvalue in the range
(of 0 to 90 °C
I (32 to 194 °F)  for
|dry-gas meter
I thermometers
Check upon receipt
for dents or bent
stem, and calibrate
(Sec. 3.4.2) against
mercury-in-glass
thermometer
 Reject  if
 unable  to
 calibrate
Barometer
(Capable of
(measuring
|atmospheric
(pressure within
(2.5 mm (0.1 in.)
JHg        :
Check against a
mercury-in-glass
barometer or
equivalent ;••	
calibrate
(Sec. 3.1.2)
 Determine;
 correction
 factor,  or
 reject  if
(difference
(more than
 ±  2.5 mm.
 (0.1 in.) Hg
Gas density
determi-
nation
equipment
(Meet the
|requirements in
 Sec. 3.2.1
Conduct checks shown
in Sec. 3.2.1,
upon receipt
 Repair, ...-'"
 replace,  or
 return to
 supplier
Sample
Recovery

Glass
sample
bottles
(Leak-free,  Tef-
|Ion lined caps,
 1000 and 100 mL
Visually.check upon
receipt for cracks,
ensure that caps are
Teflon
 Replace, or
 return to. }
 supplier
(Continued)

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                                                              Section No.  3 .19.1
                                                              Date September 3,  1992
                                                              Page 16
                                                                       o
TABLE 1.1  (Continued)
Apparatus
Sample
Preparation
and
Analysis
Glassware
AA spec-
trometer
Recorder or
electronic
integrator
Optical
cell
Aeration
cell
Moisture
removal
system
Acceptance limits
. .' r
' ' •*
"• ,"'.
Class A
Suitable optical
resolution system
and detector
See owner's manual
."•'
See Figure 1.2
. •
See Figure 1.3
.
Heated cell or
moisture trap
to remove
condensation
'
Frequency & method
of measurement -

Visually check upon
receipt
Perform appropriate
calibrations
according to Sec. 5
'_
Upon receipt, check
"
Upon receipt, check
to ensure correct
dimensions, check
heating system
Visually check
Calibrate whenever
system is turned on
Action if
requirements
are not met

.
Replace or
return to
supplier
Return to
manufacturer
or repair and
re-check
Repair or
return to
manufacturer
Return, to
manufacturer ,
clean as
needed
1
Repair or
return to
manufacturer
[Calibrate
| heated cell
|or change
desiccant
Flowmeter
Capable of
measuring flow
of 1.5 L/min
(Calibrate with
|bubble meter  or
|wet-test meter
|upon  receipt
|Return to
| manufacturer
| or repair and.
I recalibrate
                                                                                      O
system
Regulator
to remove
condensation
from ,optical cell
Proper fittings
and pressure
control
|or change
| desiccant
1
Upon receipt, | Return to
attach to cylinder (manufacturer,
and check | repair,
j or replace
| fitting and
| re-check
!
O
(Continued)

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                                                              Section No.  3.19.1
                                                              Date September 3, 1992
                                                              Page 17
TABLE 1.1  (Continued)
Apparatus
Variable
transformer
Aeration
gas
cylinder
Tubing
Trip
balance
Analytical
balance
)
'Alternative
analytical
apparatus
Sampling
and
Sample
Recovery
Reagents
1
1
| Acceptance limits
1
(Capable of varying
(voltage from 0 to
(40 volts
1
(Nitrogen or dry,
|Hg-free air equip-
(ped with regulator
1
(See Sec. 1.3.13
(for specifications
(of tubing for the
| connections
1
(Capable of
(measuring within
|0.5 g
1
(Capable of weigh-
( ing to ± 0.5 mg
1
(Capable of gene-
| rating a linear
(calibration curve;
(two consecutive
(samples of equal
(size and concen-
tration agree ± 3%
(of average; and S
| 95% recovery of
| known concentra-
tion of spiked
| sample
I
1
1
| ACS reagent grade
| or Hg blank level
| specified
Frequency & method
of measurement
Visually check
upon receipt
Visually check
upon receipt
Visually check to
ensure proper type
tubing
Check with standard
weights upon receipt
and before each use
As above
See owner ' s manual
Visually check upon
receipt or conduct
Hg analysis
Action if
requirements
are not met
Return to
manufacturer
or repair
Return to
supplier
Replace
Replace or
return to
manufacturer
As above
Return to
supplier
Return to
supplier or
replace
(Continued)

-------
                                                               Section No.  3.19,
                                                               Date September  3,
                                                               Page 18
1952
TABLE 1.1   (Continued)
     o
Apparatus
Water
Silica gel
Filter
(optional)
Analysis
Reagents
Filter
1
1
| Acceptance limits
1
(Deionized, dis-
| tilled meeting
IASTM 01193-77
I specifications
1
(indicating type,
| 6- to 16-mesh
1
(Glass fiber with-
|out organic bin-
(der; 99.95% col-
| lection efficiency
(for 0.3 urn dioctyl
Iphthalate smoke
| particles
1
(ACS reagent grade
(or equivalent;
(prepared as
(described in
(Sec. 1.5.3
1
1
1
(Whatman 40
| or equivalent
1
1
1
(Frequency & method
(of measurement
1
(check each lot or
(specify type when
(ordering
1
1
(Upon receipt, check
| label for grade
(or certification
1
| Manufacturer ' s gua-
(rantee that filters
(were tested accord-
| ing to -ASTM D 2986-
(71; observe under
(light for defects
1
1
1
(Upon receipt, check
| label for grade or
(certification; Check
(stability of
(prepared solution
(and prepare when
(necessary
1
(Upon receipt, check
| label for grade
1
Action if
requirements
are not met
Replace or
return to
supplier
Return to
supplier
Return to
supplier
Replace or
return to
supplier
Replace or
return to
supplier
                                                                                      O
                                                                                      o

-------
                                                               Section No.  3.19.2
                                                               Date September 3, 1992
                                                               Page 1
 2.0
CALIBRATION OF APPARATUS
          Calibrating  the  apparatus  is  one  of  the  more  important  functions  in
 maintaining data  quality.    The  detailed calibration  procedures  for the  sampling
 apparatus included in this section were designed for  the sampling equipment specified
 in Method  5  and  described  in the  previous  section.   Calibrating the  analytical
 equipment is  described in Section 3.19.5, which  details  the analytical  procedures.
 Table 2.1,  at the end of this  section, summarizes the quality assurance  (QA) functions
 for the  calibrations.   All calibrations,  including those performed on the analytical
 equipment}  should 'be recorded on standardized  forms and retained in a calibration log
 book.
2.1
Metering System
         The  dry-gas meter  (DGM)  in  the  sampling system's  meter console  must be
calibrated  against a  primary standard meter  (wet-test meter  or spirometer).   An
alternate procedure is to calibrate against a second reference meter (dry-gas meter or
critical orifice) that has been calibrated against a primary standard meter.

2.1.1    Wet-Test  Meter—Wet-test  meters are  calibrated by  the manufacturer  to an
accuracy of ± 0.5%.   The  calibration must be checked initially upon receipt and yearly
thereafter.  A wet-test meter with a capacity of 3.4vm3/h (120 ft3/h) or 30 L/revolution
(1 ftVrev)  will be  needed to  calibrate the  dry-gas meter.  For large wet-test meters
(>30 L/rev), there is no  convenient method for checking the calibration; consequently,
several methods are suggested,  and other methods may be approved by the Administrator.
The initial calibration may be checked by any of the following methods:
         1.    Certification  from  the manufacturer that the wet-test meter is withir.
               1% of true value at  the wet-test meter discharge,  so that only a  leak
               check of the system  is then required.
         2.    Calibration by  any primary-air  or  liquid-displacement method  that
               displaces  at least one complete  revolution of  the wet-test meter.
         3.    Comparison against  a smaller wet-test meter  that  has previously  beer.
               calibrated against  a  primary-air  or liquid-displacement method, as
               described  in Section 3.5.2 of this  Handbook.
         4.    Comparison against a dry-gas  meter  that  has previously been calibrated
               against a  primary-air  or liquid-displacement method.
         The test-meter calibration should be checked annually.  The calibration check
can be  made by  the  same method as  that  of the  original  calibration;  however,  the
comparison method need not be recalibrated if the calibration check is within 1% of the
true value.  When this agreement  is  not obtained, the comparison method or wet-test
meter must be recalibrated against a primary-air or liquid-displacement method.

2.1.2    Dry-Gas Meter as a  Calibration Standard—A DGM may be used as a calibration
standard for volume measurements in place of the wet-test meter specified in  Section
5.3 of Method 5, provided that it is calibrated initially and recalibrated periodically
as follows:

         Standard Dry-Gas Meter Calibration—The DGM to be  calibrated  and used  as  a
secondary  reference meter should  be  of  high  quality and  should have appropriate
capacity  (e.g.,  3 L/rev  [0.1  ftVrev] ) .   A spirometer  (400  L or more capacity), or
equivalent,  may be used for this calibration, although a wet-test meter is usually  more
practical.   The wet-test meter should have a capacity of  30 L/rev (1 ftVrev)  and
should  be  capable of measuring volume to  within  1.0%.   Wet-test  meters  should be


-------
                                                               Section No.  3.19.2
                                                               Date September 3, 19
                                                               Page 2
o
 checked against  a spirometer  or a  liquid displacement  meter to  ensure accuracy.
 Spire-meters or wet-test meters of other sizes may be used,  provided that the specified
 accuracies of  the procedure are maintained.  The initial calibration  may be checked by
 any  of  the following methods:
          1.   Set  up the  components as  shown  in Figure  2.1.    A  spirometer,  or
               equivalent, may be used in place of  the  wet-test meter  in  the  system.
          2.   Run the pump for at least 5 min at a flow rate of about 10 L/min  (0.35
               cfm)  to  condition the  interior  surface of  the wet-test  meter.   The
               pressure drop indicated by the manometer at the inlet side of the DGM
               should be minimized  (no greater  than 100 mm H2O [4 in.  H20]  at a flow
               rate of 30  L/min [1 cfm]).  Using large diameter tubing connections and
               straight pipe fittings will accomplish this minimization.
          3.    Collect the data as shown in  the  example data sheet   (see Figure 2.2).
               Make triplicate runs at each of the flow  rates and at  no less than five
               different flow rates.   The range  of flow  rates should  be between 10 and
               34 L/min (0.35 and 1.2 cfm)  or over  the  expected operating range.
          4.    Calculate flow rate,  Q,  for each run using  the  wet-test  meter volume
               (Equation 2-1),  Vu, and the run time, 9.  Calculate the DGM coefficient
               (Equation 2-2),  Yd., for each  run.  These calculations are  as  follows:
                                               ~T—
                     P   V
                     * bar  w                •    -
          Q   =  KI 	                                        Equation 2-1
                     (ttt + t8td)  6

                    (tds + t6td)  Pt
O
                                                                         Equation 2-2
                 Vdfi  (tw + tetd) (Pbar * Ap/13.6)

where :
         Kj   =  0.3858  for international  system of units  (SI);  17.64  for English
                 units.

         Vw   =  Wet-test meter volume,  liter (ft3).

         Vds   =  Dry-gas meter volume,  liter (ft3) .

         tda   =  Average dry-gas meter  temperature,  °C  (°F) .

         tatd  =  273 °C for SI units; 460  °F for English units.

         tw   =  Average wet-test  meter temperature,  °C (°F) .

         Pbir  =  Barometric pressure, mm Hg (in. Hg) .

         Ap   =  Dry-gas meter inlet  differential pressure,  mm H2O  (in.  H2O) .

         6    =  Run time, min.
                                                                                   O
                                                                 s* ">

-------
                                                                                                               AIR IRIET
                                                                                                    RSROnETER
\
                                                                                                                             V O CO
                                                                                                                             P P ra
                                                                                                                            (Q rt n
                                                                                                                             fl> (B ft
                                                                                                                                M-
                                                                                                                             W CO 0
                                                                                                                              (I) o
                                     Figure  2.1.  Sample meter system  calibration setup.
                                                                                                                              vr>
                                                                                                                              »r>
                                                                                                                              M

-------
Date:
Dry-gas Meter  Identification:



Barometric  Pressure  (P, ) : 	
 _in.  Hg

Approx-
imate
E low
rate
(0)
c£m
0.40

0.60

0.80

1.00

1.20

r— — i
Spiro-
meter
(wet
meter)
gas
volume
(V.)
ft'










r 	
Dry-
gas
meter
volume
(V^)
ftj







.


r
Spiro-
meter
(wet
meter)
(t.)
op










Pemperatur
I
Inlet
(t,)
oF










es
Dry-gas met
Outlet
(t,)
op
•











sr
Aver-
age












Aver-
age
meter
coef-
ficient
 O rt
        H*

     ^^§

       ^ Z
                                                                                                                    ID
                                                                                                                      O
      o
                                     Ii"u|iM'''> 2.2  Dry-c|iTn motor en 1 i brat i on  rlntn  form.
                o
o
                                                                           in
                                                                           K)

-------
                                                               Section No.  3.19.2
                                                               Date September 3,  1952
                                                               Page 5


          5.    Compare the three Yd. values at each of the flow rates and determine the
               maximum and minimum values.   The difference  between the maximum and
               minimum values at each flow rate should be no greater than 0.030. Extra
               sets of triplicate runs may be made to complete this  requirement.   Ir.
               addition,  the meter coefficients should be between 0.95 and 1.05.   If
               these  specifications   cannot  be  met  in  three  sets  of  successive
               triplicate runs, the meter is not suitable as a calibration standard and
               should not be used as  such.  If these specifications  are met,  average
               the three Yds values at each flow rate resulting in five average meter
               coefficients,  Yd..
          6.    Prepare a curve of  meter coefficient, Yd>, versus flow rate, Q,  for the
               DGM.  This curve shall be used as a reference when  the meter is used to
               calibrate  other  DGM's  and  to  determine  whether  recalibration  is
               required.

          Standard Dry-Gas Meter Recalibratioit-Recalibrate the standard DGM against a.
wet-test meter or spirometer annually  or after every 200 hours of  operation, whichever
comes  first.    This requirement  is  valid provided  the standard  DGM is  kept  in a
laboratory and, if  transported, cared for as any other laboratory instrument.  Abuse
to the  standard meter may cause  a change in the \calibration  and will require  more
frequent  recalibrations.
          As an alternative to full recalibration, a two-point calibration check may be
made.  Follow the  same procedure and equipment arrangement as for a full recalibration,
but run the meter at only two flow rates (suggested rates are 14 and 28 L/min  [0.5 arid
 .0 cfm]).   Calculate the meter  coefficients  for these two  points and compare  the
 •alues with the meter calibration  curve.  If the two coefficients are within  1.5% cf
the calibration curve values at the same flow rates, the meter need not be recalibrated
until the next date  for  a recalibration check.

2.1.3     Critical  Orifices as Calibration Standards-Critical orifices may be  used as
calibration standards in place of the  wet-test meter specified in Section 5.3 of Methcd
5,  provided that  they are selected, calibrated, and used as follows:

          Selection  of Critical Orifices—The procedure that follows  describes  the use
of hypodermic needles or stainless-steel needle tubing that have been found  suitable
for use  as  critical orifices.   Other materials and  critical orifice designs may be
used,  provided the orifices act  as true critical orifices (i.e., a critical vacuum car.
be obtained,  as  described in Section 7.2.2.2.3 of Method  5).   Select five  critical
orifices  of appropriate  size to cover the range of flow rates between 10 and  34 L/n^.n
or the  expected operating range.  Two of the critical  orifices should bracket the
expected  operating  range.
          A minimum  of three critical orifices will be needed to  calibrate a  Method 5
DGM; the  other two  critical orifices  can serve as spares, providing better selecticr.
for bracketing the  range of operating flow

-------
                                                              Section No.  3.19.2
                                                              Date September 3,  1992
                                                              Page 6

rates.  The needle sizes and tubing lengths shown below give the following approximate
flow rates:
o
Flow rate,
Gauge /cm
12/7.6
12/10.2
13/2.5
13/5.1
13/7.6
13/10.2
L/min
32.56
30.02
25.77
23.50
22.37
20.67
Flow rate,
Gauge /cm
14/2.5
14/5.1
14/7.6
15/3.2
15/7.6
15/10.2
L/min
19.54
17.27
16.14
14.16
11.61
10.48
         These needles can be adapted  to a Method 5-type sampling train as follows:
Insert a serum bottle stopper,  13-  by  20-mm (0.5-in.  by 75-in.)  sleeve type,  into a
13-mm (0.5-in.)  Swagelok™ quick-connect fitting.   Insert the needle into the stopper,
as shown in Figure 2.3.

         Initial Critical Orifice Calibration—The procedure described in this section
uses the Method  5 meter box configuration with a DGM, as  described  in Section 2.1.8 of
Method 5, to calibrate the critical orifices.  Other schemes may be used,  subject to
the approval of  the Administrator.   The critical orifices must  be calibrated in the
same configuration as they will be used  (i.e., there should be no connections to the
inlet of the orifice) .
         Prior to calibrating the critical orifices, the  dry-gas meter in the meter box
must be  calibrated.    Before calibrating  the  meter  box, leak  check the  system as
follows:
         1.   Fully  open the coarse adjust valve and  completely close  the  bypass
              valve.
         2.   Plug the inlet.
         3.   Turn  on  the  pump and determine  whether  there is  any leakage.   The
              leakage rate must be zero  (i.e., no detectable movement of the DGM dial
              must be  seen  for  1 min).
         4.   Check also for leakages in the portion of the sampling train between the
              pump and the orifice meter.  See Section 5.6 for the  procedure; make any
              corrections,  if necessary.  If leakage  is detected, check for cracked
              gaskets,  loose fittings,  worn O-rings,  etc.,  and  make  the necessary
              repairs.
O
                                                                                     o

-------
                            f
                            i
                                                 Section No.  3.19.2
                                                 Date September 3, 19S2
                                                 Page 7



J

r_-7=^
JV5 	
1
-
-



.
k 	

m ii
1 II

H V
T



1
4

r
l


CRITICAL SERUM MICK
ORIFICE STOPPER CONNECT
Critical orifice adaptation to Method 5-type metering system.
              o
                          METER BOX
                        DDDD
                      \
                    CRITICAL ORIFICE
                      Apparatus setup.


      Figure 2.3   Critical orifice and apparatus setup.

-------
                                                               Section No.  3.19.2
                                                               Date September 3,  1992
                                                               Page 8

          After determining  that the meter box is leak-free,  calibrate it according to
 the  procedure given in  Section 5.3.   Make sure that the  wet-test meter meets  the
 requirements  stated in Subsection 2.1.1.  Check the water level in the wet-test meter.
 Record  the DGM calibration  factor,  Y.   The  critical  orifice  is then  calibrated as
 follows:
          1.    Set up the apparatus as shown in Figure 2.3.
          2.    Allow a warm-up time of 15 min.  This  step  is important to equilibrate
               the temperature conditions through the DGM.
          3.    Leak check the  system as described above.   The  leakage rate must be
               zero.
          4.    Before calibrating the critical orifice, determine its suitability anc
               the appropriate operating vacuum as follows-  Turn on  the pump,  fully
               open the coarse  adjust valve,  and adjust the bypass valve to give  e.
               vacuum reading  corresponding to about  half  an  atmospheric pressure.
               Observe the meter box orifice manometer reading, AH.   Slowly  increase
               the vacuum reading until  the meter box orifice manometer shows  a stable
               reading.   Record the critical vacuum for each orifice.   Orifices  that
               do  not reach a critical value must not be  used.
          5.    Obtain the  barometric pressure using a barometer as described in Section
               2.1.9  of  Method 5.   Record the barometric  pressure,  P^,.,  in mm Hg  (in.
               Hg) .
          6.    Conduct  duplicate runs at a  vacuum of  25  to  50  ram Hg  (1 to 2  in.  He)
               above  the critical vacuum.  The runs must be at least  S  minutes  each.
               The DGM volume readings must be in increments of  complete revolutions
               of  the DGM.  As a guideline, the times should not differ by more  thar.
               3.0 s  (this includes allowance for changes  in the  DGM temperatures) to
               achieve  ± 0.5% in K'.  Record the information listed in Figure 2.4.
          7.    Calculate K'  using Equation 2-3.
                 K,  Vffl Y
                               AH/13.6)
                                           1/2
                                                                                       o
                                                                                      o
         K'
                                                                        Equation 2-3
         K'   =  Critical orifice coefficient,  [ (m3) (°K)1/2] / [ (mm Hg)
              ,   (min)H[(ftJ) (°R)1/2) ] / [ (in.  Hg)(min)]}.
where:
         Tamb  =  Absolute ambient temperature, °K  (°R).

Average the K' values.  The individual K'  values should not differ by more than
from the average.
                                                                               ± 0.5%
                                                                                     o

-------
                                                               Section No. 3.19.2
                                                               Date September 3,  1992
                                                               Page 9
Date
Train ID
Critical orifice K'  factor
Dry-Gas Meter


Final reading


Initial reading


Difference, Vm


Inlet /outlet temperatures


      Initial


      Final


      Avg. temperature, tn


Time , 6




Orifice man. rdg., A H


Bar. pressure, Pbar


Ambient temperature, tmb


Pump vacuum
Critical orifice ID
                   m3 (ft3)

                   m3 (ft3)

                   m3 (ft3)




                   °C


                   °C

                   °C

                   min/s

                   min

                   mm  (in.) H2O

                   mm  (in.) Hg


                   °C  (°F)

                   inm  (in.) Hg




                   m3 (ft3)
                                                                  Run number


                                                              1                2
DGM cal. factor, Y
                Figure 2.4.  Data sheet for determining  DGM Y  factor.

-------
                                                               Section No.  3.19.2
                                                               Date September 3.  1992
                                                               Page 10

         Using  the  Critics! Orifices &s  Calibration  Standards—The dry-gas meter  is
calibrated using the critical orifices as the secondary standard as follows:
         1.    Record the barometric pressure.
         2.    Calibrate the metering system according  to  the procedure outlined  in
               Sections 7.2.2.2.1  to 7.2.2.2.5.   Record  the  information  listed  in
               Figure 2.5.
         3.    Calculate the standard volumes of air  passed  through the DGM  and the
               critical orifices and calculate the DGM calibration factor, Y, using the
               equations below:

         Vm,.td)     =   K, V,, [PUr 4-  (AH/13.6)]/Tm                         Equation 2-4

         Vcrt.td.     =   K'  (Pb.r e)/TMbl/2                                  Equation 2-5

         Y         =   Vcrlltdl/Vm(.,dl                                       Equation 2-6

where:
         vcri«id!     =   Volume  of  gas sample  passed  through  the  critical orifice,
                       corrected to standard conditions, dscm  (dscf).
                                              -~r~
         K'        =   0.3858 °K/mm Hg for metric units
                   =   17.64 °R/in. Hg for English units.

         4.    Average the DGM calibration values  for each of  the  flow rates.  The
               calibration factor,  Y, at each of the flow rates should not differ  by
               more  than ± 2%  from the average.

         Recalibration of critical orifices—To determine the need for recalibrating the
critical orifices, compare the DGM Y factors  obtained  from  two adjacent  orifices  each
time a DGM is calibrated.  For example,  when  checking orifice 13/2.5, use  orifices
12/10.2 and 13/5.1.  If any critical orifice yields a DGM Y factor differing  by  more
than 2%  from  the others, recalibrate the critical  orifice according to the  initial
calibration procedures above.

2.1.4   Sample Meter  System-The  sample  meter system—consisting  of  the pump,  vacuum
gauge, valves,  orifice meter,  and dry-gas  meter—should be  calibrated by  stringent
laboratory  methods   before  it  is used  in  the  field.   The  calibration  should  be
re-checked after each  field test series.   This re-check is designed to provide testers
with a method that  can be used more often and  with less  effort, to  ensure  that the
calibration has  not changed.   When the quick  check  indicates that  the calibration
factor has changed,  testers must again use the complete laboratory procedure to obtain
the new  calibration  factor.   After recalibration,  the metered sample volume  must  be
multiplied by either  the  initial  or  the  recalibrated  calibration factor-that is, the
one that yields  the  lower gas volume for each test  run.
o
o
                                                                                        o

-------
 Date
Train ID
 Critical  orifice ID
Dry-Gas  Meter ."
               \
                 s~
Final  reading


Initial  reading


       Difference, Vm


Inlet/outlet  temperatures


       Initial


       Final


       Avg. temperature,  tm


Time,  8
Orifice man.  rdg.,  A H


Bar. pressure,  P^


Ambient temperature,  t


Pump vacuum


K' factor


      Average
                                                                Section No.  3 .19.2
                                                                Date September 3,  1992
                                                                Page 11
DGM cal. factor
                   m3  (ft3)


                   m3  (ft3)


                   m3  (ft3)





                   °C  (°F)
                            • ••*""*

                   °C  (°F)


                   °C  (°F)


                   min/s


                   min


                   mm  (in.) H20


                   mm  (in.) Hg


                   °C  (°F)
                           -"V

                   mm  (in'.) Hg
                                                                  Run number


                                                              1                2
                  Figure 2.5.   Data sheet for determining  K'  factor,

-------
 o
o
                                                               Section "No.  3'Yl9.2
                                                               Date September 3,  1992
                                                               Page 12

          Before calibrating the metering  system  for  the first time, conduct a  leak
 check.   The meter system should be leak-free.   Both positive  (pressure) and  negative
 (vacuum)  leak checks should be performed.  The following pressure lea'k check procedure
 will check the metering  system  from the quick-connect inlet to the orifice  outlet and
 will check the orifice-inclined manometer:                  '•        •'
          1.   Disconnect the orifice meter line from  the downstream orifice  pressure
               tap  (the  one closest to  the  exhaust of  the orifice);  plug this tap
                (Figure 2.1).
          2.   Vent to the atmosphere the negative side of the inclined manometer. If
               the inclined manometer is equipped with  a three-way valve,  this  step can
               be performed  by  turning the  valve  on  the negative  side  of the  ori-
               fice-inclined manometer to the vent position.
          3.   Place a one-hole rubber stopper with a tube through  its hole  into the
               exit of the  orifice; connect  a piece of  rubber or plastic  tubing, as
               shown in Figure 2.1.
          4.   Open  the   positive  side  of  the orifice-inclined  manometer  to  the
               "reading"   position;  if  the  inclined  manometer  is  equipped  with  a
               three-way valve,  this will be the line  position.
          5.   Plug the inlet to the vacuum pump.  If a quick-connect with a leak-free
               check valve is used on the  control module, the  inlet will not have, to
               be plugged.
          6.   Open the main valve and the bypass valve.
          7.   Blow  into the tubing  connected  to  the  end of the  orifice  until  a
               pressure of 127 to 178 mm (5 to 7 in.)  H20  has built  up in the system.
          8.   Plug or crimp the tubing to maintain this  pressure.
          9.   Observe the pressure reading for a 1-min period.  No noticeable  movement
               in the manometer  fluid level should occur.   If the meter box has a leak,
               a bubbling-type leak check solution may aid in locating it.

          After the metering  system is determined to be leak-free by the positive  leak
check procedure,  the vacuum  system  to and  including the pump should be  checked by
plugging  the  air inlet to the meter box.  If a quick-connect with a'leak-free stopper
system is presently on the meter box,  the inlet  will not have to be plugged.  Turn the
pump  on,  pull a vacuum  within  7.5 cm (3  in.)  Hg  of  absolute zero, and observe the
dry-gas meter.  If the leakage exceeds  0.00015 mVmin (0.005 f tVmin), the leak(s)  must
be found  and  minimized until the above specifications are satisfied.
          Checking  the meter system  for  leaks before  initial  calibration  is not
mandatory,  but it  is recommended.

          Note:  For  metering systems  with  diaphragm pumps,  the  normal   leak  check
procedure described above will  not detect  leakages within the pump.  For these cases,
the  following leak check  procedure  is suggested:  Make  a 10-min calibration run at
0.00057 m3/min  (0.02 ftVmin); at the  end of  the run,  take the difference  between the
measured  wet-test meter  and the dry-gas meter volumes; divide the difference by  10 to
get the leak  rate.   The  leak rate  should not exceed 0.00057 m'/rain  (0.02 ftVmin) .

          Initial calibration-The dry-gas meter and the orifice meter can be calibrate/*~N
simultaneously and should be calibrated when first purchased and any time the posttesl   )
check yields  a Y outside the range of the calibration factor Y +0.05 Y.   A calibrated
wet-test  meter (of proper size, with  -t-1%  accuracy) should be used  to calibrate the
dry-gas meter and  the orifice meter.   The  dry-gas meter  and  the orifice meter should
be calibrated in the following  manner:

-------
                                                     Section No.  3.19.2
                                                     Date September 3, 1992
                                                     Page 13

1.    Before  its initial use in the  field,  leak  check  the  metering system.
      Leaks,  if  present,  must be eliminated  before proceeding.
2.    Assemble the apparatus, as shown in Figure 2.6, with the wet-test meter
      replacing  the probe  and impingers-that  is,  with  the  outlet  of the
      wet-test meter connected to  a  needle  valve that is connected  to the
      inlet side of  the meter box.
3.    Run the pump for 15 min with the orifice meter differential (AH) set at
      12.7 mm (0.5  in.)  H20  to  allow the pump to warm up and to  permit the
      interior surface of the wet-test meter to be wetted.
4.    Adjust  the needle  valve so that the vacuum gauge on the meter  box is
      between 50 and 100  mm  (2  to  4 in.)  Hg  during calibration.
5.    Collect the  information required on the  forms provided  (Figure 2.7).
      Sample volumes, as  shown, should be used.
6.    Calculate  Y4  for  each  of the  six runs,  using the equation in Figure 2.7
      under the  Y, column,  and  record the results on the form in  the space
      provided.
7.    Calculate  the average Y (calibration factor) for the six runs using the
      following  equation:
Yl + Y2
Y3
Y4 + Y5
                                 Y6
                                                               Equation 2-7

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                                                     Section No. 3.19.2
                                                     Date September 3, 1S52
                                                     Page 14
                                                                                 o
                THERMOMETERS
       CONTROL
                                                            UTUBE
                                                          MANOMETER
    PUMP
DRY GAS METER
WET TEST METER
Figure 2.6.  Equipment arrangement for dry-gas meter calibration.
                                                                 O
                                                              _J
                                                                 o

-------
                                                                 Section No. 3.19.2
                                                                 Date September 3, 1392
                                                                 Page 15
    Date
Meter box number
1
Barometric pressure, Ph = in. Ha Calibrated by

Ori-
fice
mano-
meter
set-
ting
(AH),
in. H2O
0.5

Gas volume
Wet-
test
meter
(Vw),
ft3
5
Dry-
gas
meter
(Vd),
ft3

1.0 10
.
1.5 10
2.0 10
3.0 10
4.0
10


Temperatures
Wet-
test
meter
(tv),
oF






Drv-aas meter
Inlet

-------
                                                              Section No. 3.19 .2
                                                              Date September 3, 1992
                                                              Page 16
Nomenclature:

         Vw    =   Gas  volume passing through the wet-test meter,  ft3.

         Vd    =   Gas  volume passing through the dry-gas meter,  ft3.

         tw    =   Temperature of  the gas in the wet-test meter,  °F.

         tdl    =   Temperature of  the inlet gas of the dry-gas meter,  °F.

         tdo    =   Temperature of  the outlet gas of the dry-gas meter,  °F.

         td    =   Average temperature of the gas in the dry-gas meter, obtained by the
                  average tdl  and tdo ,  °F.

         AH    =   Pressure differential across orifice,  in.  H20.

         YJ     =   Ratio of accuracy of  wet-test meter to dry-gas meter for each run.
                  Tolerance  Y, = Y ± 0.02 Y.

         Y     =   Average ratio of accuracy of wet-test meter to dry-gas meter for all
                  six  runs.   Tolerance  Y = Y ± O.Ol Y.

         AH@,   =   Orifice  pressure  differential  at each  flow rate that  gives  0.75
                  ftVmin of air at standard conditions for each calibration run, }
                  of H2O.   Tolerance = AH@ ± 0.15  (recommended).
 o
o
         AH@  =  Average orifice pressure differential that gives 0.75 ftVmin of air
                 at standard conditions  for all  six runs,  in. H20.  Tolerance =1.84
                 ± 0.25  (recommended).

         6    =  Time  for each  calibration  run,  min.

         Pt.    =  Barometric pressure,  in. Hg.
       Figure 2.7.   Dry-gas meter calibration data  (English units, backside).

-------
          10.
                                                Section No. 3.19.2
                                                Date September 3, 1992
                                                Page 17

Record the average on Figure 2.7 in the space provided.
Clean, adjust, and recalibrate, or reject the dry-gas  meter  if one or
more values of Y fall outside the interval Y ± 0.02 Y.   Otherwise,  the
average  Y is  acceptable  and  should  be  used for  future checks  and
subsequent test runs.
Calculate AH@, for each of  the six  runs using the  equation  in Figure
2.7A or 2.7B under the AH@j column, and record on the form in the space
provided.
Calculate'the average AH0 for the six runs using the following equation:
  AH@1
                               AH03 + AH@4 + AHS5 -t- AH@6
                                                                         Equation 2-8
               Record the average on Figure 2.7 in the space provided.
          11.   Adjust the orifice meter or reject  it  i'f'^H@i varies by more than ± 3.9
               mm (0.15 in.) H20  over the range of 10 to 100 mm (0.4 to 4.0 in.) K50.
               Otherwise, the average AHS  is  acceptable-arid should be used  for sub-
               sequent test runs.                 	  „ ....  <, ....,

          Posttest   calibration   check—After  each  field  itest   series,   conduct   a
metering-system  calibration check,  as specified in Subsection 2.1.4, except  for the
following variations:
          1.    Three calibration runs at a  single intermediate orifice meter setting
               may be used with the vacuum  set at a maximum value reached during the
               test series.  The single  intermediate orifice meter setting should be
               based on the previous field test.  A valve must be inserted between the
               wet-test meter and the  inlet  of  the  metering system to  adjust  the
               vacuum.  "     "         '"   •  --v    •	     '...., ..,..,,_  ,__i
          2.    If a temperature-compensating dry-gas meter was used,  the calibration
               temperature meter must be within ±  6 °C (10.8 °F)  of the average merer
               temperature during the test series.
          3.    Use Figure 2.8 to record the required information.
          If  the  calibration factor  Y deviates by <5% from the  initial  calibration
factor  Y,  then  the  dry-gas meter  volumes  obtained during  the  test   series  are
acceptable.  If  Y deviates by >5%,  recalibrate the metering system and use whichever
meter coefficient (initial or recalibrated) yields the  lowest gas  volume for each test
run.
          Alternate procedures (e.g., using  the orifice meter coefficients or critical
orifices) may  be used.

-------
                                                              Section No.  3 .19.2
                                                              Date September 3, 1992
                                                              Page 18
                                                                      o
Date
             Metering System ID No.
Barometric pressure, Pb =
Ori-
fice
mano-
meter
set-
ting
AH
in. Hg

'Spiro-
meter
(wet


.
Temperatures
| Spiro-
test) | Dry-gas
gas
meter

meter 1 Dry-qas meter
(wet |
volume (volume (meter)

-------
 2.2
                                                               Section No.  3.19.2
                                                               Date September 3, 1992
                                                               Page 19
Temperature Gauges
 2.2.1    Impinger Thermometer—The thermometer used to measure the temperature of the
 gas  leaving the impinger train should initially be compared with a mercury-in-glass
 thermometer that  meets ASTM E-l No.  63C or  63F specifications.  This procedure is as
 follows:
          1.    Place both the  reference thermometer and the test  thermometer  in an ice
               bath.  Compare  readings after they stabilize.
     ^-   2.    Remove the thermometers from the  bath and  allow  both to come to room
               temperature.  Again, . compare  readings after they  stabilize.
          3.    Accept the test thermometer if its reading agrees  to within 1  °C (2 °F)
               of the reference  thermometer reading at  both temperatures.    If the
               difference is  greater than  1  °C  (2 °F),  the thermometer should be
               adjusted and  recalibrated until  the criteria are  met, or it should be
               rejected.   Record  the results on Figure  3.1 of Section 3.19.3.

 2.2.2  Dry-gas Thermometers—The  thermometers used to  measure the metered gas sample
 temperature should be compared initially with a mercury-inglass  thermometer as above,
 using a similar procedure.
          1.    Place the dial type (or equivalent1}" thermometer and the mercury-in-glass
               thermometer in  a hot  water bath, 40 to 50 °C  (104 to 122 °F).   Compare
               the readings after  they stabilize.
          2.    Allow both thermometers to come to room temperature.  Compare readings
               after thermometers  stabilize.
          3.    Users should accept the dial type (or equivalent)  thermometer under the
               following  conditions: The values must agree to within 3 °C (5.4 °F) at
               both points; the temperature  differentials  at  both points are within 3
               °C  (5.4 °F), and the temperature differential is taped to the thermome-
               ter and recorded on the pretest  sampling check form (Figure 3.1).
          4.    Prior to  each  field trip,   compare  the temperature  reading  of the
               mercury-in-glass thermometer  at room temperature with that of  the meter
               system thermometer.   The values or corrected values should be within 6
               °C  (10.8 °F) of one another, or the meter thermometer should be replaced
               or  recalibrated.   Record any temperature correction factors on Figure
               3.1 of Section  3.19.3 or on a similar  form.

2.2.3     Stack Temperature Sensor—The stack temperature  sensor  should be calibrated
upon receipt or checked before field use.   Each  sensor should be uniquely marked for
 identification.  The calibration should be  performed at three points and then extra-
polated over the  range of temperatures anticipated during actual sampling.   For the
three-point calibration,  a reference ASTM mercury-in-glass thermometer should be  used.
         The following  procedure is recommended for  calibrating stack temperature
sensors (thermocouples and thermometers) for field use.
          I.    For the ice-point calibration, form a slush from crushed  ice and liquid
               water (preferably deionized,  distilled)  in  an insulated vessel  such as
               a  Dewar flask.   Taking care  that they do  not touch the sides of the
               flask,  insert  the  stack temperature sensors into the slush to a  depth
               of  at least 2 in.  Wait 1 min to achieve thermal equilibrium and record
               the readout on  the potentiometer.  Obtain three readings  taken at  i-min
               intervals.
                    Note:  Longer  times may be required to attain thermal equilibrium
               with thick-sheathed thermocouples.

-------
Section No. 3 .19 .2
Date September 3,
Page 20
                                                                     ^™^
                                                                     V   J
Fill a large  Pyrex beaker with water to a depth >4  in.   Place  several
boiling chips in the water and bring the water to a full boil  using a
hot plate as the heat source.
     Insert the stack temperature sensor (s)  in the  boiling water  to a
depth of at least 2 in., taking care not to  touch the  sides  or bottom
of the beaker.
     Place an ASTM reference  thermometer alongside  the  sensor (s) .   If
the entire  length  of  the mercury shaft  in  the thermometer  cannot  be
immersed, a temperature correction './ill be required to give the correct
reference temperature.
     After 3  min,  both  instruments will  attain thermal equilibrium.
Simultaneously record temperatures from the ASTM reference  thermometer
and the stack temperature sensor three times at 1-min intervals.
For thermocouple, repeat Step  2 with a  liquid  (such as cooking oil)  that
has a boiling point in the  150 to 250 °C (300 to 500 °F) range.   Record
all data on  Figure 2.9.   For thermometers  other than  thermocouples,
repeat Step 2 with a  liquid that  boils at the maximum  temperature  at
which the thermometer  is to be used, or place the stack thermometer and
reference thermometer  in a furnace or other device to reach the required
temperature .                    -«~
Note: If the thermometer is to be  used at  temperatures higher than the
reference  thermometers  can  record,  the  stack  thermometer  may  be
calibrated with a  thermocouple previously calibrated with  the  above^—. .
procedure .                                                           {   )
If the absolute values of the  reference thermometer and thermocouple (sV_X
agree to within 1.5% at each of the  three  calibration points, plot the
data on  linear  graph paper  and  draw the best-fit  line to  the  three
points or  calculate  the constants  of the linear  equation  using  the
least -square method.   The data may be  extrapolated above and below the
calibration points to cover the entire manufacturer's  suggested range
for the  thermocouple.   For the portion of  the plot or equation  th&-
agrees within 1.5%  of  the absolute reference temperature, no correcticr.
need be made.  For all portions that do not  agree within 1.5%,  use the
plot or equation to correct the data.
     If  the  absolute  values  of  the  reference  thermometer  and  stack
temperature sensor (other  than the  thermocouple) agree to  within 1.5%
at each of  the three points,  the thermometer  may be used over the ranee
of  calibration  points  for  testing without  applying  any  correcticr.
factor.  The data cannot be extrapolated outside the calibration points.

-------
Date
Ambient temperature

Calibration person
                 Thermocouple No.
                  °F  Barometric pressure
                 Reference: mercury-in-glass
                            other
                                                            Section No. 3.19.2
                                                            Date September 3, 1992
                                                            Page 21
                                     in. Hg
                                         op
                                         oF
Reference
point
number
|Source"
j(specify)
I
(Reference
I thermometer
|temperature,
 OF
I
I Thermocouple
|potentiometer
I temperature,
I Temperature*
I difference,
1%
 Type of calibration system used.

  (ref temp,  °F + 460) -  (test thermom temp, °F + 460)  x 10Q _      (
-------
                                                               Section  No.  3.19 .2
                                                               Date September 3, 19S2
                                                               Page 22
                                                                                    o
2.3       Probe  Heater
          The probe heating system should be calibrated prior to field use according to
 the procedure outlined  in APTD-0576.  Probes constructed according to APTD-0581 need
 not be  calibrated  if  the curves of APTD-0576 are used.

 2.4       Barometer            ..>•„,                     -

          The field barometer should be adjusted initially' and before each test series:
 to agree  to within 2.5  mm  (0.1  in.)  Hg of the mercury-inglass barometer or with the
 station pressure value reported by a nearby National Weather Service station, corrected
 for elevation.   The correction  for elevation difference between the station and the
 sampling  point  should be applied at a rate of -2.4 mm Hg/30 m  (-0.1 in.  Hg/100 ft).
 Record  the  results on the pretest sampling check form (Figure 3.1  of Section 3.19.3).

 2 .5       Probe  Nozzle

          Probe  nozzles should be calibrated before initial  use in  the field.  Using a
 micrometer, measure  the ID  of the  nozzle to  the nearest 0.025 mm (0.001 in.).  Make
 three measurements using different diameters each time, and obtain the average.  Tne
 difference  between the high and the low numbers  should not  exceed  0.1 mm (0.004 in.
 When nozzles become nicked, dented, or corroded, they should be reshaped,  sharpened,^
 and  recalibrated  before  use.    Each  nozzle   should  be  permanently  and  uniquely
 identified.  Figure 2.10 is an example of a nozzle calibration data form.

 2.6       Pitot  Tube

          The Type  S  pitot  tube assembly should  be calibrated using  the procedure
 outlined  in Section 3.1.2 of this Handbook for Method 2.

 2 .7       Trip Balance

          The trip  balance  should be calibrated  initially  by using  Class  £ standard
weights and should be within 0.5  g of  the  standard weight.  Adjust  or  return the
balance to  the  manufacturer if limits are not met.
                                                                                   O

-------
                                                                Section No.  3.19.2
                                                                Date September 3,  1992
                                                                Page 23
I/Date
                     Calibrated by
Nozzle
ID No.

Nozzle Diameter*
mm (in.)
1
mm (in.)

im (in.)
'
~f~
\
ADb
mm ( in . )
-
1
mm ( in . )

where :
8 EI.;, 3 = Three different nozzle diameters, mm (in. ; each diameter must be measured
  AD
within (0.025 mm) 0.001  in.
Maximum difference between any two diameters, mm (in.), AD <(0.10 mm) 0,004
in.
Average of D,,  D;, and  D3.
                      Figure  2.10.   Nozzle calibration data form.

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                                                              Section No.  3.19.2
                                                              Date September 3,  1992
                                                              Page 24
               TABLE 2.1.  ACTIVITY MATRIX FOR EQUIPMENT CALIBRATION
o
Apparatus
Wet-test
meter
Dry-gas
meter
Critical
Thermo-
meter
Probe
heating
system
Barometer
Acceptance limits
Capacity S3. 4
mVh (120 ftVh);
accuracy within
± 1.0%
Yj = Y ± 0.02 Y
K' = K i 0.03 K'
Impinger thermo-
meter ± 1 °C (2
°F) ; dry-gas meter
thermometer ± 3 °C
(5.4 °F) over
range ; stack
temperature sensor
± 1.5% of absolute
temperature
Capable of
maintaining 120 °C
± 14 °C (248° ± 25
°F) at a flow rate
of 20 L/min
(0.71 ft'/min
± 2.5 mm (0.1 in.)
Hg of mercury-in-
glass barometer
Frequency & method
of measurement
Calibrate initially,
and then yearly by
liquid displacement
Calibrate vs.
wet-test meter
initially, and when
posttest check
exceeds Y ± 0.05 Y
Calibrate vs. wet,
dry, or~ bubble meter
upon receipt and
after each test
Calibrate each ini-
tially as a separate
component against a
mercury-in-glass
thermometer; then
before each trip
compare each as part
of the train with
the mercury-in-glass
thermometer
Calibrate component
initially by APTD-
0576; if constructed
by APTD-0581, or use
published calibra-
tion curves
Calibrate initially
vs. mercury-in-glass
barometer; check
before and after
each field test
(Action if
| requirements
| are not met
1
(Adjust until
| specifications
(are met, or
jturn to
(manufacturer
1
(Repair, or
| replace and then
(recalibrate
1
1
(Repair and then
| recalibrate,
(or replace
1
(Adjust;
(determine
|a constant
(correction
| factor;
(or reject
1
1
1
(Repair, or
| replace and
(then reverify
(the calibration
1
1
(Adjust to agree
(with a certified
(barometer
1
1
                                                                                       O
(Continued)
                                                                                      o

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TABLE 2.1.   (Continued)
                                                              Section No. 3.19.2
                                                              Date September 3, 1992
                                                              Page 25
Apparatus
I
(Acceptance limits
|Frequency  & method
I of measurement
I Action if
|requirements
I are  not met
Probe
nozzle
(Average of three
|ID measurements of
(nozzle; difference
(between high and
| low SO . 1 mm
I(0.004 in.)
|Use  a micrometer  to
(measure  to nearest
(0.025 mm (0.001 in.)
I
                                        I
(Recalibrate,
I reshape,  and
I sharpen when
(nozzle becomes
(nicked, dented
|corroded
Trip
balance
|500-g capacity;
|capable of  measur-
|ing within  ± 0.5  g
(check with standard
(class S weights upon
(receipt
(Adjust,  replace
(or return to
I manufacturer

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o
o
o

-------

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o
                                                                Section  No. 3.19.3
                                                                Date September 3, 1992
                                                                Page 1
   3.0
               PRESAMPLING OPERATIONS
O
               This section addresses preparing and packing sampling supplies and equipment.
      The pretest preparations form  (Figure 3.2 of Method 5, Section 3.4.3)  can be used as
      an equipment checklist, a status form, and a packing list for Methods  1-4 and Method
      101A.  The (QA)  activities for the  presampling operations are summarized in Table 3.1
      at the end of this section.
               A pretest  check will have  to be made  on  most of the  sampling apparatus.
      Figure 3.1 should be used to record the pretest calibration checks.  A schematic of the
      EPA Method 101A sampling train is shown  in Figure  1.1.  Commercial models  of this
      system are available.   Each train must be in compliance with the specifications of the
      reference method, Section 3.19.10.
           Apparatus Check and Calibration
      3 .1
3.1.1    Nozzles and Pi^Jf^yH^fST^MasplSft^idheaffifiga^J^dn should be checked to see
that it  is  operating  properly.   The probe should be  sealed at  the  inlet or  tip and
checked  for leaks at a vacuum of 380-mm  (15 in.) Hg, and the probe must be leak-free
under these  conditions.   The nozzles  should be~ calibrated  using the  procedures  in
Subsection 2.5 of Section 3.19.2.  Clean the probe ,and the nozzle's internal  surfaces
using the procedures described  abdP«3>{§im8egSi©ii S323si^e^fia§3$f aHReT?tB&*saa«ap]Hhe
ends of  the nozzle should be sealed with a Teflon film.   _
                                                        •ou           saA
3.1.2    Filter #oldeirf/UStojIiW£
-------
(f
                                                                 Section  No.  3.19.3
                                                                 Date September 3, 1992
                                                                 Page 3

    3.1.7     Bare/neter-The  field barometer should be compared with  the mercury-in-glass
    barometer or the weather station reading,  after making an elevation correction, prior
    to  each  field trip.

    3 .2       _Sample Recovery Equipment and Reagents

             Clean all sample exposed-glassware using the following procedures:
             1.    Soak glassware in 50%  HN03 for a minimum of 1 h.
             2.    Rinse  with tap water.
             3.    Rinse  with 8  N HCl.
             4.    Rinse  with tap water.
             5.    Rinse  with DI water.

    3.2.1     Glass  Sample  Bottles—The  sample  bottles  must  be leak-free,  must  gave
    Teflon-lined caps, and must  be  1000 and 100 mL in size.

    3.2.2     Graduated Cylinder—A 250-mL graduated cylinder is required.

    3.2.3     Funnel an'd Rubber Policeman—These items aid in transferring the silica gel to
    the container; they are not  necessary if the silica gel is weighed in the field.
  I"
    3.2.4     Funnel—A glass funnel  is required to aid in sample recovery.

    3.3       Equipment Packing                                                  ,

             The accessibility,  condition, and functioning of measurement devices in the,
    field depend  on  packing them  carefully and on  moving  them carefully at  the site.
   Equipment should  be  packed to withstand severe  treatment  during  shipping  and field
   operations. The material used to construct shipping cases is therefore important.  The
   following containers are suggested, but they are not mandatory.

   3.3.1     Proie—Seal the inlet and outlet of  the probe to protect it from breakage and
   pack it  in the container.   An  ideal container  is a wooden case  (or  the equivalent)
   lined with  foam  material  and having  separate  compartments to hold the individual
   probes.   The case should have handles  or eye-hooks that can withstand hoisting and that
   are rigid enough to prevent  bending or twisting during shipping and handling.

   3.3.2     Impingers,  Connectors,  and Assorted Glassware-All  impingers  and  glassware
   should be packed in rigid containers and protected by polyethylene or other suitable
   material.  Individual compartments for glassware will help to organize and protect each
   piece.

   3.3.3     Volumetric Glassware-A sturdy case lined with foam material can contain dryir.g
   tubes and assorted volumetric glassware.

   3.3.4    Meter Box—The meter box, which contains the manometers, orifice meter, vacuum
   gauge, pump, dry-gas  meter,  and thermometers, should be packed in a shipping  container
   unless its housing is sufficient to protect components during travel.  Additional puz.p
   oil should be  packed if  oil  is  required.  A spare meter box should  be  included  in case
   of failure.

   3.3.5     Wash Bottles  and  Storage Containers-Storage containers  and  miscellaneous
   glassware should be packed  in -a rigid, foam-lined container.

-------
                                                               Section  No.  3.19.3
                                                               Date September 3, 1992
                                                               Page 4

3.3.6    Chemicals-Chemicals should be packed in a rigid, foam-lined container.
         As mentioned in Subsection 1.5.1.6   (Absorbing  Solution, 4% KMn04) , caution
must be  exercised  for the  storage and transport of KMnO<.   To prevent autocatalytic
decomposition of the permanganate solution, filter it through Whatman 541 filter paper.
The  reaction  of the KMnO4 with  the  acid may  cause  pressure buildup  in  the sample
storage bottle.  These bottles should not be filled to capacity and should  be vented
to relieve excess pressure and to prevent explosion of the sample.  A No. 70-72 hole
drilled in the container cap and Teflon liner is recommended.
         Also, caution should be exercised with the HC1  reagent because it  is highly
corrosive. .  •                                             '' '       '     .
                 '                            •          '     •   t. ••!":'':.      j
                    j                                                "
3.3.7    Safety  Equipment  for Sampling Train Preparation and Sample Recovery-Safety
glasses and protective laboratory gloves should be packed for the personnel assigned
to prepare the sampling  train and recover the sample.  Serious  injury can result from
contact with HC1 and KMn04.
o
                                                                                    o
                                                                           X
                                                                          X

-------
                                                               Section  No.  3.19.3
                                                               Date September 3,  1952
                                                               Page 5
                TABLE 3.1  ACTIVITY MATRIX FOR PRESAMPLING OPERATIONS
Apparatus
Apparatus
Check and
Calibration
Nozzles
and
probe
liners










1
(Acceptance limits
1
1
1
1
1
|l. Probe heating
| system capable of
| heating to 120 °C
|± 14 °C at a flow
jrate of 20 L/min
1
| 2 . Probe leak free
jat 380-mm (15 in.)
(Hg
1
|3. Nozzles
(calibrated
| (Sec. 3.19.2
I Subsec . 2.4)
1
1
(Frequency & method
| of measurement
!
1
1
1
1
|l. Check heating
(system initially and
(when moisture cannot
|be prevented during
(testing
1
| 2 . Visually check
(before test
1
1
|3. Before -test to
(nearest O.D25-irun
(with micrometer
1
1
Action if
requirements
are not met



1 . Repair or
replace



2 . Replace



3. Recalibrate,
reshape, or
replace


                (4. Probe and
                (nozzle free of
                |contaminants
                j(Sec. 3.2)
                I
                         14. Clean internally
                         (by brushing with tap
                         (water, deionized
                         (distilled water, and
                         (acetone; air dry
                         (before test
                          |4. Repeat
                          |cleaning and
                          |assembly
                          |procedures
                          I
Impingers,
filter
holders,
and other
glassware
(Meets specifica-
|tions in Subsec.  1
(of  Sec.  3.19.1;
|cleaned  according
|to  Sec.  3.19.3
|Subsec.  3.1.2;  and
(sealed with
(Teflon or glass
|stoppers
 Before  each  test
                                                   (Repair or
                                                   (discard and
                                                    replace
Dry-gas
meter
(clean and readings
(within 2% of
|average
(calibration factor
                         (Calibrate according
                         (to Sec. 3.19.2
                                        I
                           Repair or
                           replace and  ther
                           recalibrate
Filters
|Free of
|irregularities
(visually  check prior
(to testing
                                                   (Replace
(Continued)

-------
TABLE 3.1   (Continued)
                                                               Section  No.  3.19.3
                                                               Date September  3, 1992
                                                               Page 6
                                                                                   o
Apparatus
               I
               (Acceptance limits
                         (Frequency  & method
                         I of measurement
                          (Action if
                          [requirements
                           are not met
Silica gel
               (indicating, 6-16
               |mesh, use fresh-
               |or dry-used silica
               (gel at 175 °C
                (350 °F)
                         I If moisture content
                         |is to be determined,
                         (weigh several 200-
                         jto 300-g portions of
                         (silica gel
                         11 (± 0.5 g); use
                         (airtight containers;
                         |record weight of
                         (container plus
                         (silica gel
               (calibrated, within      (Calibrate against
                                        |mercury-in-glass  •
                                        |thermometer
                                        I(Sec. 3.4.2)  before
                                        | each
                           Replace or
                           reweigh
Thermo-
meters
   °C (2 °F)  for
|impinger thermo-
lmeter,  ± 3  °C
I (5.4 °F)  for
(dry-gas meter
|thermometer
                                                    Replace
                                                                                   O
Barometer
(Calibrated,  within
J2.5-mm (0.1  in.)
(Hg
(calibrate  against
| mercury-in-glass
(barometer  (Sec.
j 3 .7 .2)  before  each
test
Replace
Sample
Recovery
Equipment
and
Reagents

Glass
sample
bottles

Graduated
cylinder
               (Clean, leakless,
               (Teflon-lined caps
               (clean, glass and
               (class A; 250 mL
               (with <2 mL
               I subdivisions
                         (Before each field         (Replace
                         (test                      I
                         I                           I
                         I                           I
                         (Before each field         (Replace
                         |trip check for            |
                         (cracks,  breaks,  and       |
                         (manufacturer flaws         |
Funnel
               (Clean, glass,
               (Class A
                          Same as above
                           Same as  above
                                                                                    O
(Continued)

-------
                                                              Section  No.  3.19.3
                                                              Date September 3, 1992
                                                              Page 7
TABLE 3.1  (Continued)


Apparatus
Equipment
packing
Probe


Impingers ,
connectors,
and
assorted
glassware
Volumetric
glassware





Meter box





Wash
bottles
and
storage
containers
Chemicals



Acceptance limits


Rigid container
protected by
polyethylene foam
Rigid container
protected by
polyethylene foam


Packed in original
containers, if
available, or a
rigid container
lined with foam
and marked
•Fragile"
_|
Meter box case
and/or additional
material to
protect train
components; pack
spare -meter box
Rigid foam-lined
container



Rigid foam-lined
container

I Frequency & method
of measurement


Prior to each
shipment

Prior to each
shipment



Prior -ifb each
shipment \





Prior to each
shipment




Prior to each
shipment



Prior to each
shipment
[Action if
requirements
are not met


Repack


Repack




Repack






Repack





Repack




Repack

                         Y

-------
o
o
o

-------
                                                            Section No. 3.19.4
                                                            Date September 3, 1992
                                                            Page 1
 4.0   ON-SITE MEASUREMENTS
       On-site activities include transporting the equipment to the test site, unpacking
 and assembling  the  equipment,  sampling  for particulate and gaseous mercury,  and
 recording  the data.  The associated QA activities are summarized in Table 4.1 at the
 end of this  section.

 4.1 Transport of Equipment to the Sampling Site

       The most efficient means of transporting the equipment from ground level to the
 sampling site (often above ground level) should be decided during the preliminary site
 visit  or  by prior correspondence.   Care should  be  taken  to prevent damage  to:the
 equipment  or injury  to .test personnel during the moving.  A clean "laboratory type"
 area free of excessive dust and mercury' compounds should be located and designated for
 preparing  the nozzle, probe, filter holder, and impingers and for sample recovery.

 4.2  Preliminary Measurements  and Setup

       A preliminary survey should be conducted prior  to  sampling and analysis, unless
 adequate prior knowledge of the source is available.  Testing must be conducted at the
 proper sampling locations and during the proper process and control equipment operating
 cycles or  periods.   Testers  should  refer to  Subsection  3.19.3.1 for  information
 ypically needed to establish  the proper sampling and analysis protocol.
       Testers should have calculated the minimum sampling run time required, unless it
 is known that the minimum time  stated  by the applicable regulations will be sufficient
 to provide proof of compliance.
       In this method, highly oxidizable matter may make it impossible to sample for the
 desired minimum  time.   This problem  is  indicated by the complete bleaching of the
purple color of the KMnO4 solution.  In these cases, testers may  divide the sample run
 into two or more subruns to ensure that the absorbing solution will not be depleted.
 In cases where excess water condensation is encountered,  collect two runs to make one
 sample.                                       •••.•-.,

 4.2.1  Preliminary Measurements and Setup-The sampling  site  should be  selected in
accordance with Method 1.  If  the duct configuration or some other factor makes this
 impossible, the site should be approved by the Administrator, prior',to conducting the
 test.  A 115-V, 30-A electrical supply is necessary to operate the standard sampling
train.   Either measure the stack and  determine the minimum number of.;traverse points
by Method 1,  or check the traverse points determined during  the preliminary site visit
 (Section 3.0) .   Record all  data on the traverse point location,form shown  in Method 1.
These measurements will  be used to locate the pitot tube and the  sampling probe during
preliminary measurements and actual sampling.

-------
                                                            Section No. 3.19,
                                                            Date September 3,
                                                            Page 2
1992
o
 4.3   Preparations  for Sampling
       The  most  common  situations and problems are addressed in  this  section.   Both
 required and recommended  QA/control  checks and procedures are  provided to assist in
 collecting data of acceptable quality and  to assess the accuracy of the sampling and
 analysis.
       On-site sampling includes  the  following steps:
       1.     Conducting preliminary measurements and setting up the recovery area.
       2.     Preparing and setting up the sampling system for leaks.
       3. Connecting electrical service and checking the sampling system for leaks.
       4.     Heating the probe and filter to the proper temperature.
       5.     Inserting the probe  into the duct and sealing the duct.
       6.     Isokinetic sampling.
       7.     Recording data.
       8. Posttest leak check of  the sampling system.
       9.     Recovering the sample and transporting it to the laboratory.

 4.3.1   Stack Parameters-Check the  sampling site for cyclonic or nonparallel flow as
 described  in Method 1  (Section  3.0).   The sampling site must be acceptable before a
 valid  sample can be taken.  Determine the  stack~rpressure, temperature, and the range
 of velocity  heads encountered  (Method  2) .   Determine the moisture content using the
 approximation Method 4,  or its alternatives, for the purpose of  setting the isokinetic
 sampling rate.  If the identical source has been tested before or if a good estimateX^X
 of the moisture content  is available, this  should be sufficient.  The reference methodt    )
 (Section  3.4.10)  uses  the  condensate  collected during  sampling to  determine the
 moisture content used in final  calculations.   If the  stack is saturated with moisture
 or has water  droplets, the moisture content must also be determined by partial pressure
 with the use of a more accurate  stack gas  temperature sensor (Method 4).
       Determine the dry molecular weight  of  the stack gas,  as  required in Method 2.
 If an  integrated gas sample is required, follow Method 3 procedures and take the gas
 sample simultaneously with,  and for the same total  length of  time, as  the particulate
 run.   The  sampling and the analytical data forms for molecular weight determinations
 are in Method 3.
      Using the stack parameters obtained by these preliminary measurements,  the tester
 can set up the nomograph as  outlined in APTD-0576 or  use  a calculator.  An example of
 a nomograph  data form is.shown in Figure 4.1 of the Method 5, Section 3.4.4.
      Select a nozzle size  based on the range of velocity  heads,  so  that it is not
 necessary  to change the  size to maintain  isokinetic  sampling  rates  during thev>run.
 Install the  selected nozzle using a Viton A O-ring  when glass liners are used.   Other
 connecting systems such  as  Teflon ferrules may be used.  Mark  the  probe with heat
 resistant  tape or by some other  acceptable method to denote the  proper distance into
 the stack  or duct for each sampling point. Select a total sampling time greater than
or equal to  the minimum total sampling time specified in the test procedures for the
 specific industry so that:
       1. The  sampling  time  per  point  is  >2 min  (a greater  time interval  may be
         specified by the Administrator).
      2. The  sample  volume  corrected  to  standard  conditions  exceeds  the required
         minimum total gas sample volume.
      The  latter  can be  based  on  an  approximate  average  sampling  rate.    Its-
recommended  that the number of minutes sampled at each point be  either an  integer o"
an integer plus one-half  minute  to  avoid timekeeping errors.  In some circumstances
 (e.g.,  batch cycles),  it  may be  necessary to sample  for  shorter times-  at the traverse
    D

-------
                                                            Section No. 3.19 .4
                                                            Date September 3, 1992
                                                            Page 3

points and to obtain smaller gas sample volumes.   In these cases, the Administrator's
approval must be obtained  first.

4.3.2  Sampling Train Preparation—During preparation of the sampling train, keep all
openings where contamination can occur covered until just prior to assembly or until
sampling commences.  The glassware  should have  been  cleaned as described in Section
3.19.3 by soaking in 50% HNO, and then rinsing with tap water,  8 N HC1, tap water, and
finally deionized distilled water.  Prepare the individual sampling train components
as follows:
         Impinqers
      1. Place 50 ml of fresh 4% KMnO4 in the first cleaned impinger using a graduated
         cylinder that has been properly cleaned,
      2. Place 100  ml  of  fresh 4%  KMn04  in  the  second and third  impingers  using a
         graduated cylinder, and
      3. Place 200 to 300  g of preweighed silica gel in the fourth impinger.
      Precaution:  It is extremely important that all.sample recovery personnel wear
safety glasses and  gloves  due  to  the  dangers associated with impinger solutions and
recovery solutions.
      Record the weight of  the silica gel and the container on the sample recovery data
form, Figure 4.1,  or other similar data form. -'"Place  the empty container  in a safe
place for use later  in the sample recovery.  If moisture content is to be determined
by impinger analysis, weigh each of the first three impingers to the nearest  0.5 g, and
record these weights.  Place the silica gel container in a clean place for later use
in the sample recovery.   Alternatively, the weight of the silica gel plus impinger may
be determined to the nearest 0.5 g and recorded.

-------
                                                            Section No. 3.19 .4
                                                            Date September 3, 1992
                                                            Page 4
  o
Plant 	 Sample Data
Sample Location 	 Run No. 	
Sample Recovery Person 	 Recovery Date
Filter(s) No. 	
                                      MOISTURE

Impinqers
Final volume  (wt)       	 ml  (g)     Final wt    	 g 	 g
Initial volume  (wt)     	 ml  (g)     Initial wt  	 g 	 g
Net volume  (wt)         	 ml  (g)     Net wt      	 g 	 g
      Total moisture    	 g

                               RECOVERED SAMPLE BLANK

Blank filter Container No. 	KMnO4 added, sealed and level marked?	
Blank KMnO4  solution (650 mL) Container No. 	 Sealed and level marked? 	
Blank HC1 solution  (25 mL added to 200 mL H2O) Container No. 	
 Sealed and level marked? 	
                                  RECOVERED SAMPLE
KMn04 impinger contents and rinse (400 mL) Container No.	
 Sealed and level marked? 	
Filter Container No.  	  KMnO4 added, sealed and level marked?


HCl solution  (25 mL  added to 200 mL  H,O) Container No. 	
 Sealed and level marked? 	

Samples stored and locked? 	
Remarks: 	
O
Date of laboratory custody 	
Laboratory person taking custody
Remarks: 	
                Figure 4.1.   Sample recovery and integrity data form.

-------
                                                            Section No. 3.19.4
                                                            Date September 3, 1992
                                                            Page 5

      The  use of  a filter  is  optional in  Method 101A.   However,  because  of the
digestion  techniques used for  sample  preparation,  it is  highly  recommended that a
falter be  used.  Assemble the filter holder as follows:
         Filter  (optional)
      1. Using a tweezer  or  clean disposable surgical gloves,  place a filter in the
         filter  holder.   Be  sure that the filter  is  properly  centered and that the
         gasket  is properly placed to prevent the sample gas stream from circumventing
         the  filter.
      2. Visually check the  filter for damage after the assembly is completed.
      3. The  filter  or filter sample container should be marked.
      Record  the filter  number  on the sample recovery data form  and  then place the
filter sample container in a clean place for later use in the sample recovery.
      Assemble the probe and nozzle as follows:
      Probe/nozzle assembly
      1. The  probe  liner  should be glass and cleaned using the procedures described
         above.
      2. Place the properly sized, calibrated,  and cleaned nozzle on the inlet of the
         probe using a Teflon ferrule or Viton O-ring connection.
      The nozzle should be uniquely identified.  Record the nozzle number and diameter
on the sampling  data form.                    -*~
                                                  \
4.3.3  Sampling  Train Assembly—Assemble  the  train'as  shown in  Figure  1.1, using (if
necessary)  a very light coat of silicone grease only on the outside of all ground-glass
joints to avoid  contamination.  The tester may find that it is beneficial to conduct
a leak check of the. sampling  train in  the assembly area prior to taking the system to
the;stack.
      The sampling train  is then transported to the stack.  At the stack, place crushed
ice and water around the impingers.   If not already an  integral part  of the probe
assembly,  a temperature sensor should  be attached to the metal sheath of the sampling
probe so that the sensor  extends  beyond the  probe tip and does not  touch any metal.
The sensor's position should  be  about 1.9 to 2.54  cm (0.75 to 1 in)  from the pitot tube
and the nozzle to avoid interference with the gas flow.  Alternative arrangements are
shown in Method  2.

4.3.4  Sampling Train Leak Checks—Leak checks are necessary to assure that the sample
has not been biased  low  by  dilution air.   The reference  method  (Section 3.19.10)
specifies that leak  checks be performed at certain times as discussed below.
      Pretest—A  pretest leak check is  recommended, but  not required.   If the tester
opts to conduct  the  pretest  leak check, follow the procedure described below:
      After the sampling train has been assembled, set  the filter heating system at the
desired operating temperature.   Allow time for  the temperature to  stabilize.  If a
Viton A O-ring or other leak  free gasket is used in connecting the  probe  nozzle to the
probe liner,  leak  check the train at  the sampling site  by plugging  the nozzle and
pulling a  380- mm  (15 in) Hg vacuum.   Note:  A lower  vacuum may be used if it is not
exceeded during  the  test.
      If an asbestos string is used for the probe gasket,  do not connect the probe to
the train during the leak check.  Instead,  leak check  the  train by first plugging the
inlet to the  filter holder and pulling a 380-mm  (15  in)  Hg vacuum  (see note in the
previous paragraph) .  Then connect the probe to the train and leak check at  about  25-iran
(1 in.)  Hg vacuum; alternatively, the probe may be leak checked with the  rest of the
sampling train in one step at a 380-mm  (15 in.) Hg vacuum.  Leakage rates >4% of the
average sampling rate  or 0.00057 mVmin  (0.02 ftVmin) , whichever  is  less, are
unacceptable.

-------
                                                            Section No. 3.19.4
                                                            Date September 3, 1992
                                                            Page 6

      The following leak check instructions for the sampling train are taken from APTD-  \)
05813 and APTD-0576.  Start the pump with the bypass valve fully open and the coarse
adjust valve closed.  Open the  coarse  adjust valve  and then slowly close the bypass
valve until the desired vacuum is  reached.  Do not reverse the direction of the bypass
valve; this will  cause  KMnO4  solution  to back up from the impingers into the filter
holder.  If the desired  vacuum is  exceeded, either leak check at  this higher vacuum or
end the leak check as described below and start over.
      When the leak check is complete,  first  slowly  remove the plug from the inlet to
the probe or the filter holder and then close the coarse adjust valve and immediately
turn off the vacuum pump.  (This prevents the KMnO4 in the  impingers from being forced
back into the filter holder and prevents the silica gel from being forced back into the
third impinger.)  Visually check to be  sure KMn04 did not contact the filter and that
the filter has no tears before beginning the sampling.
      During the Sampling—If. a component (e.g., filter assembly or impinger) change is
necessary during the sampling run, a leak-check should be conducted before the change.
The leak-check should be done according to the procedure outlined above,  except that
it should be at a vacuum equal to or greater than the maximum value recorded up to that
point in the test.  If the leakage rate is <0.00057 mVmin (0.02  ftVmin) or 4% of the
average  sampling rate   (whichever  is  less),  the  results  are  acceptable,  and  no
correction need be applied to the total volume>~of dry gas metered.   If,  however,  a
higher leakage rate is obtained,  the  tester either>should  record  the leakage rate and
plan to correct the sample volume as shown in Section 6.3(b) of the Reference Method
(Section 3.19.10), or should void the sampling run.   Note: Be sure to record the dry
gas meter reading before and after each  leak-check performed during and after each test
run so that the sample volume can be corrected.
      Posttest—A leak-check is mandatory at the conclusion of each sampling run.  The
leak-check should be in  accordance with the procedures in this section and at a vacuum
equal to or greater than the  maximum value reached  during the  sampling run.   If the
leakage rate  is <0.00057  mVmin  (0.02  ftVmin)  or  4% of the average  sampling rate
(whichever is less),  the results are  acceptable,  and no correction need be applied to
the total volume of dry gas metered.  If, however, a  higher leakage rate is obtained,
the tester either should record the leakage rate and correct the  sample volume as shown
in Section 6.3(a) or 6.3(b) of the Reference  Method  (Section 3.19.10), or should void
the sample run.   Note:  Be  sure  to record  the dry gas meter reading before and after
performing the leak check  so that the sample volume can be corrected.

4.3.5  Sampling Train Operation—Just prior to  sampling, clean the portholes to minimize
the chance  of  sampling  deposited material.   Verify  that the  probe and  the filter
heating systems are up  to the desired temperatures  and  that the pitot  tube and the
nozzle are located properly.  Follow the procedures below for sampling.
      1. Record the initial  dry gas meter readings,  barometric pressure,  and other
         data as indicated in Figure 4.2.
      2. Position the tip of the probe  at the first sampling point with the nozzle tip
         pointing directly into the gas stream.  When in  position, block off the open
         area  around  the  probe  and  the porthole to prevent flow  disturbances and
         unrepresentative  dilution of the gas stream.
      3. Turn on the pump and immediately adjust the sample  flow to attain isokinetic
         conditions.  Nomographs, calculator programs, and routines are available to
         aid in the rapid determination of the orifice pressure  drop  corresponding to
         the isokinetic sampling rate.   If the nomograph is designed as  shown  in APTD-
         0576 it can be used only with  an Type S  pitot tube which has a Cp coefficient
         of 0.85 ± 0.02  and when  the stack  gas dry  molecular weight (Ms) is 29 i 4.
         If Cp and Ms  are outside these ranges, do not use  the  nomograph without
o
X""X
f   J
^—

-------
                                                      Section No.  3.19.4
                                                      Date September 3,  1992
                                                      Page 7

   compensating  for  the differences.   Recalibrate  isokinetic  rate or reset
   nomograph if the absolute stack temperature (Ts) changes more than 10%.
4. Take other readings  required by Figure 4.2 at  least once  at  each sampling
   point during each time increment.
5. Record the dry gas meter readings at the end of each time increment.
6. Repeat steps 3 through 5 for each sampling point.
7. Turn off  the  pump,  remove the  probe  from the stack,  and  record  the final
   readings after each traverse.
8. Conduct  the  mandatory  posttest  leak check  (Subsection  4.2.5)  at  the
   conclusion of  the  last traverse (after  allowing  the nozzle to cool).  Record
   any leakage rate.   Also,  leak check the pitot  lines (Method 2, Section 2.1);
   the lines must pass this leak-check to validate the velocity pressure data.
9. Disconnect the probe, and then cap the nozzle and the end of the probe with
   polyethylene or equivalent caps.

-------
Plant 	
City 	
Location 	
Operator 	
Date 	
Run No. 	
Stack dia. mm  (in).
Sample box No.
Meter box No.
Meter AH@ 	
Meter calibration  (Y)
Pitot tube  (Cp)   	
Probe length 	
Probe liner material
Probe heater setting
Ambient temperature _
Barometric press  (Pb)
Assumed moisture  	
Static press. (Pa) 	
C Factor 	
Reference AH@
            Sheet      	
            Nozzle ID No.
of
         ft Nozzle diameter 	
         	  Thermometer No. 	
         	  Final leak rate 	
         °F Vacuum during leak-check
            iron (in)
       m3/min (cfm)
      	 mm (in) Hg
 mm (in)  Hg Filter No(s).
	 %H2O Remarks:	
 mm (in)  Hg
traverse
point
number


















Sampling
time,
(6) , min









\

[_..





Total
Clock
time,
(24 h)











._






Vacuum,
mm
(in) Hg

















Max
Stack
temp
(Ts)
°C (°F)






•










Avg
Velocity
head
(APs)
mm
(in) Hg


















Press
across
orifice
meter
(AH) , mm
(in) Hg

















Gas sample
volume (Vm) ,
m3 (ft3)




"J
--











(Total
i
Dry gas meter
temperature
Inlet | Outlet
°C(°F) °C(°F)


































Avg | Avg
Gas temp
leaving
impinger
°C(°F)

















Max
Filter
temp
°C(°F)












0> D»  rr
1 CD > o
..._. *rt a
H
L. ^M
OJ «>
L-
                                                                                                                   ID
                                                                                                                   to
                                  Figure 4.2.   Method 101A field sample data form.
      o
                           o
                                               o

-------
                                                      'Section 3.19.4
                                                      Date April 3, 1992
                                                      Page 9          -i

       During  the test run,  a sampling rate  of  10% of the  isokinetic  rate must be
 maintained unless otherwise specified by the Administrator.  The sampling rate must be
 adjusted  at any  sampling  point  if  a  20% variation  in velocity pressure occurs.
       Periodically during the test, observe the connecting glassware—from the probe,
 through the filter, to the first impinger—for water condensation.  If  any is  evident,
 adjust the probe  and/or  filter  heater  setting  upward  until  the  condensation is
 eliminated; add  ice around the  impingers  to maintain the  silica gel exit  temperature
 at  20  °C  (68  °F).                           :         -
       The manometer  level and ; zero  should also  be checked  periodically during  each
 traverse. Vibrations  and temperature  fluctuations can cause the  manometer  zero to
 Shift.      "                        ->   '  -c- '•••   .....--:.     .     ,:

 4 .4 Sample Recovery

       The reference method (Section 3.19.10) requires that  the sample be recovered from
 the probe, from all glassware preceding the filter, from the  front  half of the filter
 holder, from  the filter,  and from the impingers and connecting glassware in an  area
 sheltered from wind  and dust to prevent  contamination  of the  sample.  Begin proper
 cleanup procedure as  soon as the probe is  removed from the  stack  at  the end of  the
 sampling period.  Allow the probe to  cool.  When-art  can be safely handled,  wipe off any
 external particulate matter near the tip of the probe nozzle,  and place a cap over it.
 Do not cap off the probe  tip  tightly while the sampling train is cooling because the
 resultant vacuum could draw liquid out  from the  impingers.  Before moving the sample
 train  to  the  cleanup site, remove the probe from the  train, wipe off  the  silicone
 grease, and cap the open  outlet of the  probe  and the inlet of the  sample  train.
       Be  careful not  to  lose any condensate that might  be present.   Wipe  off  the
 silicone grease from  the impinger.  Use  either ground-glass stoppers, plastic caps, or
 serum  caps  to close  these openings.   The capped-off  impinger box  .and the capped
 sampling  probe  can be  transported  to  the cleanup area  without risk  of losing or
 contaminating the sample.  Transfer the probe, impinger assembly, and  (if  applicable)
 filter assembly to a  cleanup area that is clean,  protected from the wind,  and free of
 Hg contamination.  The ambient  air in  laboratories located in the  immediate  vicinity
 of Hg-using facilities  is not normally free of Hg contamination.  Inspect  the  train
 before and during disassembly,  and note any abnormal conditions.             .->,.,;••._.
      Precautions  It is  extremely important  that  all sample recovery personnel wear
 safety glasses and gloves due to the dangers associated with impinger solutions and
 recovery solutions.                                     ..-".-••!•
      The following sample recovery sequence includes (1)  recovery-of  the sample from
 the impingers using KMnO<, Container 1;  (2)  recovery of any residual brown deposits
 from the impingers  using water,  Container  1;  (3)  recovery of the sample from the probe
 and connecting glassware using KMnO«,  Container No.l;  (4)  recovery of  any  residual
 brown deposits from the probe and connecting glassware using water, Container No.l; (5)
 recovery of any  residual  brown deposits  from sample train components not removed by
water with HC1, Container 1A;  recovery of  silica  gel. Container 2; (6)  recovery of the
 filter, Container No.  3;  (7) collecting a. filter blank, Container No.,4,; (8) collecting
an KMnO< reagent blank, Container No. 5; (9) collecting a water reagent blank, and (10)
 collecting a HC1 reagent  blank.

 4.4.1  Impinger Contents  (Container  Nos.  1 and 1A)—Recover the samples  follows: c
      1. Note the color of the  reagent  in each of  the impingers and record  the color
         on the  Sample  Recovery Data  Form.   If the color of  the  KMnO« in  the last
         impinger has changed from the purple  color, the sample run  will  be considered
         invalid and  must  be  repeated.  •• If all the impinger  solution   has  been

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 o
                                       .               Section 3.19.4        .--.-<
                          -••  "                        Date April 3, 1992
                                                      Page 10

         oxidized,  the tester should  (1)  reduce the  sample  time or volume  if the
         reduced time  or volume will comply with the applicable regulations,  (2) add
         another impinger  containing KMnO<, or  (3)  use  two sample trains per sample
         run.
      2. Using a properly cleaned graduated cylinder,  measure  the  liquid in the first
         three impingers to within  1 ml.   Record the  volume of liquid on the Sample
         Recovery and  Integrity Data Form.   This information  is needed to calculate
         the moisture content of the effluent gas.   (Use only  graduated cylinders and
         glass storage bottles 'that have been precleaned as in Section 3.19.3.)
      3. Place  the  contents of  the first  three impingers  in a  properly  cleaned,
         1000-ml glass sample bottle (Container  No.  1).  Record the data on the sample
         recovery data form.
      4. Prior to recovering the  sample,  place  400-ml of fresh KMnO« in a graduated
         cylinder for  sample recovery.  This solution is used to recover sample from
         the probe nozzle, probe  fitting,  probe liner,  and front half of the filter
         holder  (if applicable) and impingers  (sample-exposed surfaces).   Rinse the
         impingers with  a portion  (about  100 ml)  of  the 400 ml  of fresh 4%  KMnO<
         solution  to  assure  removal  of  all  loose  particulate matter   from  the
         impingers; add all washings to the 1000-ml glass sample bottle (Container No.
         1) .
      5. To  remove  any  residual  brown  deposits;  on  the  glassware following  the
         permanganate  rinse, carefully  rinse all the  sample-exposed glassware with
         approximately 100 ml  of water.   Add this rinse  to  Container No.  1.   The
         impingers should only require about 50 ml of the 100 ml of water.
      6. If no visible deposits remain after this water rinse, do not rinse with 8 N
         HC1.  However,  if deposits remain on  the  glassware  after the water rinse,
         place 25 ml  of  8 N HC1  in a  graduated cylinder.  Wash impinger walls and
         stems with this  25  ml of  8 N HCl  as  follows:  Place  150 ml of water in a
         sample container labeled Container No.  1A.   Use only  a total of  25 ml of 8 N
         HCl to rinse all impingers. Wash the impinger walls and stem with the HCl by
         turning and  shaking  the  impinger so that  the HCl  contacts all  inside
         surfaces.   Pour the HCl wash carefully  while  stirring into Container  No. 1A.
         Rinse all glassware that was exposed to HCl with 50 ml water, and add water
         rinse to Container  No.  1A.  Label the  sample  bottle and record the sample
         number on the Sample Recovery Data Form. The separate container is used for
         safety reasons.

4.4.2   Probe  and  Connecting  Glassware  (Container No.  Ij-The  same  sample bottle
(Container No. 1) as used above for the  impinger contents and  sample  rinse is  usually
adequate for the  collection of all the rinses. Recover the sample from the probe  liner
and connecting glassware as follows:
      1. Clean the outside of  the probe, the pitot tube,  and the nozzle to  prevent
         particulates  from being brushed into the sample bottle.  Take care  that dust
         on the outside of the probe or  other exterior surfaces does  not  get into the
         sample during the quantitative recovery of the  Hg  (and any  condensate) from
         the probe nozzle, probe  fitting,  probe liner,  and front half of the filter
         holder  (if applicable).
      2. Carefully remove the probe nozzle and rinse the inside surface (using a ny
         bristle brush and several KMnO< rinses)  into the sample bottle (Container1- No f
         1) .
      3. Clean the  compression fitting by  the same procedure.  Rinse all sampleexposed
         glassware components with  the total of 400 ml  of  fresh 4% KMnO< solution  as
O

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                                                        Section 3.19.4
                                                        Date  April  3, 1992
                                                        Page  11

           measured above.   Add  these washings to  the 1000-ml glass sample  bottle
           (Container No. 1).
        4. After the KMnO4  rinse,  use  a small  portion of  the  remaining  100  ml  of water
           to rinse the  nozzle and connecting glass after  the KMnO4  rinse.  Add the
           rinses to Container 1.
        The following  probe rinsing procedure should  be performed by two people  to
  preclude sample  loss.   The  rinsing  procedures  for the probe liner and  connecting
  glassware is as follows:
        1. Rinse the probe  liner by tilting and rotating the probe while squirting fresh
           4% KMnO4  solution into  the upper  (or nozzle) end to  assure complete wetting
           of the inside surface.
        2. Allow the KMnO, solution to drain into the sample  bottle  (Container  1) using
           a funnel to prevent spillage.
        3. Hold the probe  in an  inclined position  and squirt  KMnO4 solution  into the
           upper end while  pushing the probe  brush through  the liner with  a  twisting
           motion,  and catch the  drainage  in  the sample bottle.  Repeat the  brushing
           procedure three  or more times until a visual inspection of the  liner reveals
           no particulate remaining  inside.
        4.    Rinse the liner once more with KMn04 solution.
        5. Rinse the brush with KMn04 solution into^Container 1 to remove all  sample that
           is retained by the bristles.             >
        6.    Rinse the probe liner with the remaining 100 ml of water into Container 1.
        7. Wipe all  the connecting joints clean of silicone grease, and clean the  inside
           of the front half of the filter holder by rubbing the surface with a nylon
           bristle  brush  and rinsing it with KMn04.  Repeat the procedure at  least three
           times or until no particles  are  evident  in the rinse.
        8. Make a final rinse of  the  filter holder  and brush.
        9. Clean any connecting glassware which precedes the  filter  holder,  using Steps
           5 and 6.
        After all washings have been collected  in Container No.  1, tighten the lid on the
  container to prevent leakage during shipment  to the laboratory. It is recommended that
  the  lid have  a  No.  70-72  hole  drilled  in the container cap and Teflon  liners for
  pressure relief.   Mark the height of the fluid  level  to  determine whether leakage
  occurs during transport.   Label the  container to identify its contents clearly, and
  note  it on the Sample Recovery  Data  Form.

  4.4.3  Silica Gel  (Container No.  2)—Note  the  color  of the indicating silica  gel  to
  determine whether it  has  been completely  spent, and make a  notation of  its condition
  on the sample recovery  data form,  Figure  4.3.
        1.    Transfer  the  silica gel from the  fourth impinger to its original container
              using a  funnel and a rubber policeman, and seal the container.  It  is not
              necessary to  remove  the small amount of dust particles that  may adhere to
              the impinger wall;  since the  weight  gain  is  used for moisture  calcula-
              tions,  do not use water  or other liquids to transfer  the  silica  gel.
        2.    Determine the  final weight gain to the nearest  0.5  g,  if  a  balance  is
              available.

  4.4.4  Filter ("Container  No.  3)-Carefully remove the filter (if used)  from the  filter
  holder,  place it  in a 150-ml glass sample bottle,  and  add  20 to 40 ml of 4% KMnO^ to
    merge the  filter.   If it  is  necessary to  fold the  filter,  be sure  that the
'articulate cake is inside the fold.   Carefully transfer, to the 150-ml sample bottle,
  any particulate matter and filter fibers that adhere to the  filter holder gasket by
  using a dry Nylon bristle brush and a sharp-e|dged blade.  Seal the container.   Clearly

-------
                                                      Section 3.19.4
                                                      Date April 3, 1992
                                                      Page 12

label the container to identify its contents.  Mark the height of the fluid level to
determine whether leakage occurs during transport.

4.4.5  Filter Blank (Container No.  4)—If. a filter is used for testing, initially take
an unused filter for each field test  series  and label  as  a filter blank.   Treat the
filter blank in the same manner as described in Subsection 4.3.4 above.

4.4.6  Absorbing Solution Blank (Container No. 5;-For a  blank, place 650 ml  of 4% KMn04
absorbing solution in a  1000-ml  sample bottle.   If the 100 ml  water rinse was used
during recovery, carefully add a second 100  ml portion of  water to Container No. 5.
It is recommended that the lid have a  No.  70-72 hole drilled in the container cap and
Teflon liners for pressure relief.  Mark the height  of the fluid level  to determine
whether leakage occurs during transport.  Label the container  as the  KMnO4  blank,  and
seal the container.

4.4.7  8 N HC1 Blank (Container No.  6)-It 8 N  HCl was used (Container 1A) to remove any
residual brown deposits remaining after rinsing sample-exposed glassware with fresh 4%
KMnO, solution and  water,  place 25  ml  of 8 N HCl used for removing the deposits in a
separate sample container  (Container No. 6) containing 200 ml of water. Mark container
as the HCl blank, and seal the container.      -f~
                                                   \
4.5  Sample Logistics and Packing Equipment

      Follow the sampling and sample recovery procedures until the required number of
runs are completed  and blank  samples are labeled.  Log all data on the Sample Recovery
and Integrity Data Form,  Figure 4.1.  At  the conclusion of the test:
      1. Check all  rinses and filters  for proper labeling  (time,  date, location, test
         run number,  and any  other pertinent documentation)  .  Be  sure  that blanks have
         been set aside and labeled.
      2. If possible,  make a copy of the field data form(s) in case the originals are
         lost.
      3. Examine all sample  containers  for damage and  ensure  that they  are properly
         sealed for transport to the base laboratory.   Ensure  that the containers are
         labeled properly for  shipping to prevent  loss of  samples or equipment.
      4. Review the field  sampling data  form  and any  other  completed data forms to
         ensure that all data  have been recorded  and that  all forms are present.

4.6  Systems Audit

      A Method 101A sampling  and sample  recovery checklist is presented in Figure  4.3.
o
o
                                                                                       o

-------
                                                           Section  3.19.4
                                                           Date April  3, .1992-
                                                           Page 13
     Date 	 Time    •    Operator 	 Observer
                               Method 101A Sampling  Procedures
     Probe Nozzle:  stainless steel  	 glass
           Button-hook 	elbow	 size
           Cleaned according to sampling protocol? 	__
           Sealed with Teflon tape or other cover?	
     Probe  liner:  borosilicate 	 quartz _________ other
           Cleaned according to sampling protocol? 	"
           Openings sealed with Teflon  tape?	
           Probe heating system:
           Checked?  	 Temperature 	 Stable?

     Pitot  tube:  Type  S 	  Other 	
           Properly  attached  to  probe  (no  interference to nozzle)?
           Modi f i cat ions: 	;	
           Pitot tube  coefficient 	\	
ijpjpjjj/ Differential  Pronsure Gauge:  Inclined manometers
          Magnahelics 	 Ranges 	
          Other 	 Ranges 	
    Cyclone  (inlet only): borosilicate glass 	 other
          Cleaned according  to  sampling protocol? 	
    Filter Holder: borosilicate  glass 	 other
          Frit material: glass 	 Teflon	 other
          Gasket material:  silicone	 other 	
          Cleaned according to sampling..protocol? 	
          Sealed with Teflon tape or glass  caps?	
    Filter type (a):	
          Cleaned according  to  sampling protocol?

    Impinger Train: number of impingers 	
          Cleaned according  to  sampling protocol?
          Contents: 1st 	 2nd 	  3rd
                    4th 	 5th 	  6th
          Impinger weights recorded?	;	
          Proper connections?	—
          Modifications	
    Silica gel: type 	 new? 	 used?
    Figure 4.3.  Field observation of Method  101A  sampling  and  recovery.

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                                                      Section 3.19.4
                                                      Date April 3, 1992
                                                      Page 14
o
 Date 	 Time 	 Operator 	 Observer
                           Method 101A Sampling Proceduren

 Procedure

 Barometer: mercury 	aneroid 	 other 	
Can Doncity Determination: temperature sensor
      pressure gauge 	
      Temperature sensor properly attached to probe? 	

Recent Calibrations: pitot tubes 	
      meter box	 thermocouples/thermometers

Filters checked visually for irregularities? 	
Filters properly centered? 	 labelled?

Sampling site properly selected?	

Nozzle size properly selected? 	
Proper sampling time selected or calculated?
All openings of sampling train sealed  (pretest
      and posttest)?  	
Impingers, filter holder, probe, and nozzle assembled?

Cyclone attached (inlet only)? 	
Pitot lines checked for leaks and plugging?
Meter box leveled? 	 Manometers  zeroed?

AH@ from most recent calibration 	
Nomograph setup correctly? 	 K factor
Pretest leak-check conducted? 	__Leakage rate?

Care taken to avoid scraping nipple or stack wall? 	

Effective seal around probe when in-stack? 	
Probe moved to traverse points at proper time?
     Figure 4.3. (Contined)
O
o

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                                                      Section 3.19.4
                                                      Date April 3, 1992
                                                      Page 15
Date
             Time
Operator
Observer
                           Method 101A Sampling Proccduroo
Nozzle and pitot tubes kept parallel to stack at all times?
Filter(s) changed during run? 	
      Any particulate lost during filter change?


Data forms completed and data recorded properly?
Nomograph  setting  changed  with  significant  change  in  the  stack  temperature?
Velocity pressure and orifice pressure recorded.accurately?
                                               —r**

                                 	 Leakage rate	
Posttest leak-check conducted?
      at inches of mercury 	
Orsat analysis?
                            Stack
                  Integrated
Approximate stack temperature


Percent isokinetic calculated


Comments 	
                                      Gas sample volume
        Figure 4.3.   (Continued)

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                                                      Section 3 .19.4
                                                      Date April 3,  1992
                                                      Page 16
Date 	 Time 	 Operator 	 Observer
                           Mothod 101A Sample  Rocovory
Reagentc:

Bruohoo: Teflon bristle 	 other 	
      Cleaned according to sampling protocol? 	
Waoh bottloo: glass 	  other 	
      Cleaned according to sampling protocol? 	

Storage containoro:  glass? 	   other?  	
      Cleaned according to sampling protocol? 	
      Teflon cap liner?	 Leak free?
      Small hole in cap to relieve pressure? 	
Filter containorc: borosilicate glass 	 other
      Cleaned according to sampling protocol?  -~
Graduated cylinder: borosilicate glass 	 other
      Subdivisions of graduated cylinder <2 ml? 	
      Cleaned according to sampling protocol? 	
Balance typo: 	Calibrated?

Probe allowed to cool sufficiently? 	
Probe and sample train openings covered?

Clean-up area(s) used 	
KMnO4 Volume:  Was 400 mL of KMnO< measured  for recovery?
Filter handling: tweezers used? 	 surgical gloves?
      Any particulate lost? 	
      KMnO<  added to filter? 	
Probe handling: KMn04 rinses 	 Brushed?
      H,O rinses 	 Brushed? 	
Rocovory of probo: probe nozzle 	 probe fitting
      probe liner 	front half of filter holder _

        Figure  4.3.   (Continued)
                                                                                  o
o
                                                                                  o

-------
                                                        Section 3 .19.4
                                                        Date April 3, 1992
                                                        Page 17
  Date 	 Time 	 Operator            . Observer
                          Method 101A Sample Recovery (cont)

  HC1 Volume: Was 25 mL of HC1 measured for recovery?	
  Xmpingor handling: weighed? 	 volumed?
        KMn04  rinses 	 H2O rinse 	
        HC1 rinses	
  Blankn collected: filter
        KMnO<  (650  mL) 	
        HC1 (25 mL in 200 mL of H2O)
  Container No. 1: Sample No. 	   400 mL KMnO4  rinse.
        Impinger contents	  Impinger Rinse 	
        Probe rinse 	 Nozzle rinse 	^Z	
  Container No.  1A: Sample No.  	   25 mL HCl
        Impinger rinse
11 'v
   ontainer No.  2 Silica gel:  color? 	 condition? 	  weighed?
  Samples labeled and stored properly?

  Liquid levels marked? 	

  Remarks:	__
         Figure 4.3.   (Continued)

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                                                      Section 3.19.4
                                                      Date April 3, 1992
                                                      Page 18
                                                                 o
             TABLE 4.1.   ACTIVITY MATRIX FOR ON-SITE MEASUREMENT CHECKS
Apparatus
  Acceptance limits
Frequency and method
   of measurement
Action if
requirements
are not met
Preliminary
determinations and
measurements
Determine the
moisture content of
stack gas
                   Determine  flow rate
                   of stack gas

                   Determine  stack
                   temperature

                   Determine  stack
                   dimensions

                   Determine  dry
                   molecular  weight of
                   stack gas
                   Select sampling time
                   S minimum total sam-
                   pling time in
                   applicable emission
                   standard; number of
                   minutes between read-
                   ings should be an
                   integer
Once each field test;
use wet bulb/dry bulb
thermometer,'Method 4,
or sling psychrometer

Once each field test,
using Method 1

Prior to and during
sampling

Prior~to sampling,
using tape measure

Once each field test,
Method 2; if inte-
grated gas sample is
required, Method 3

Prior to sampling
Complete
                                               Complete


                                               Complete


                                               Complete


                                               Complete
                  O
                                               Complete
Preparation of
collection train
 Assemble train
 according to
 specifications in
 Figure 1.1 and Sec.
 3.18.4 Subsec. 4.3.3

 Leak-check; Leak
 rate < 4% or 0.00057
 mVmin (0.02  ft3/
 min) ,  whichever is
 less
Before each sampling
run
Complete
                                          Leak-check before sam-
                                          pling by plugging the
                                          nozzle or inlet to
                                          first impinger and by
                                          pulling a vacuum of
                                          380 mm  (15 in) Hg
                        Correct the  leak
                                                                                   O
(Continued)

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                                                            Section 3.19.4
                                                            Date April 3, 1992
                                                            Page 19
X^N
©
TABLE 4.1   (Continued)
      Apparatus
                     Acceptance limits
Frequency and method
   of measurement
Action if
requirements
are not met
      Sampling
      (isokinetically)
                    Within 10% of
                    isokinetic condition

                    Standard check for
                    minimum sampling
                    time and volume;
                    sampling time/point
                    S 2 min

                    Minimum number of
                    points specified by
                    Method 1
                          Leak-check; leakage
                          rate < 0.00057 mV
                          min (0.02 ftVmin)
                          or 4% of the average
                          sampling volume,
                          whichever is less
Calculate for each
sample run

Make a quick calcu-
lation before each
test, and exact cal-
ulation after
Check before the first
test run by measuring
duct and using Method
1
    —i™~
Leak-check after each
test run1 or before
equipment replacement
during test at the
maximum vacuum during
the test (mandatory)
Repeat the test
run

Repeat the test
run
Repeat the pro-
cedure to comply
with specifica-
tions of Method 1

Correct the
sample volume,
or repeat the
sampling
      Sample recovery
                    Sample free of
                    contaminat ion
Transfer sample as
outlined in Sec 3.19.
4, subsec 4.5 after
each test run; label
containers and mark
level of solution in
container
Repeat the
sampling
      Sample logistics
      and packing of
      equipment
                    All data recorded
                    correctly
                          All equipment
                          examined for damage
                          and labelled for
                          shipment

                          All sample contain-
                          ers and blanks
                          properly labelled
                          and packaged
After completion of
each test and before
packing; if possible,
make copies of forms

After completion of
each test and before
packing
                                          Visually check upon
                                          completion of each
                                          sampling
Complete data
                                                                  Repeat sampling
                                                                  if damage occurred
                                                                  during the test
                        Correct when
                        possible

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o
o
o

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                                                               Section No.  3.19.5
                                                             '  Date September 3,  I9B2
                                                               Page 1


 5.0      POSTSAMPLING OPERATIONS

          The postsampling  operations  include postsampling  calibration  checks of
 sampling equipment and analysis by atomic absorption spectrophotometry techniques. The
 sample  analysis  includes  calibrations  and  performance  checks.    Checklists for
 monitoring the postsampling operations are provided at the end of this section.   Table
 5.1 at  the  end of  this  section summarizes  the  QA activities  associated with the
 postsampling operations.

 5.1      Calibration Checks of Sampling Equipment

          Posttest checks will have to be made on most of the sampling apparatus.   These
 checks will include three  calibration runs at a single orifice meter setting, cleaning,
 and/or routine maintenance.  Cleaning and maintenance are discussed in Section 3.19.7
 and in APTD 0576.   Figure 5.1  can be used to record the  posttest  checks.

 5.1.1     Metering   System—The  metering  system  has  two  components  that  must b=
 checked-the  dry-gas meter and  the dry-gas  meter thermometer(s).
          The dry-gas  meter  thermometer(s)  should  be compared  with  the  ASTM  mer-
 cury-in-glass thermometer at room temperature.  If the two readings agree within 6 CC
 (10.8  °F) , they are acceptable; if not,  the thermometer must be  recalibrated according
 to Subsection 2.2 of Section 3.19.2 after the posttest  check of the dry-gas meter. Fcr
 calculations,  use  the dry-gas meter  thermometer  readings  (field or recalibraticr.
 values)  that would  give the higher temperatures.':'That is, if  the  field readings are
 higher,  no correction  is necessary, but' if the rec'alibra'tion value is  higher, add the
 difference .in the two  readings to the  average dry-gas meter temperature reading.
          The posttest  check of the dry-gas meter is  described in Section 3.19.2.  The
 metering system should not have  any  leaks that were corrected prior to the  posttesr
 check.   If the dry-gas meter calibration factor  (Y) deviates by <5% from the initial
 calibration  factor,  the  dry-gas meter volumes obtained during  the test series are
 acceptable.  If Y deviates by  >5%, recalibrate the metering system (Section  3.19.2;.
For the calculations, use  the calibration factor (initial  or recalibration) that yields
 the lower gas volume for  each  test run.

 5.1.2     Stack  Temperature  Sensors—The stack  temperature  sensor readings  should be
compared with the reference thermometer readings.
         For thermocouple (s),  compare the thermocouple and reference thermometer values
at ambient temperature.  If the values agree within  1.5%!of  the absolute temperature,
the calibration is considered valid.   If the values  do not agree within 1.5%, recali-
brate the thermocouple as  described in Section 3.19.2  to determine  the difference  (A75
at the average stack temperature (T.) .  NOTE:  This  comparison may be done  in the  field
 immediately  following  the tests.
         For thermometers, compare the  reference thermometer:
          1.   At ambient  temperatures  for average stack temperature below 100 °C (212

-------
                                                               Section No. 3.19 .5
                                                               Date September 3, 1992 /"""N
                                                               Page 2                 I    )
 Plant	 Calibrated by
 Meter box number 	 Date    	
Dry-Gas Meter

Pretest calibration factor, Y                    .. ..          (within 2%)
Posttest check, Y*                           (within 5% of pretest value)
Recalibration required?                    ' yes  ____________________ no
      If yes, calibration  factor, Y	  (within 2%)
Lower calibration factor,  Y	 for calculations  (pretest or posttest)

Dry-Gas__ Meter Thermometers

Was a pretest temperature  correction used? 	yes  _   	no
      If yes, temperature  correction 	  (within 5.4 °F over range)
Posttest comparison with mercury-in-glass thermometer?  * (within 10.8 °F at ambient
      temperature) 	,	 °F
Recalibration required? 	yes  	  _no
Recalibration temperature  correction?   '     (within 5.4  °F over range)
      If. yes, no correction necessary for calibration if meter thermometer temperature
      is higher, if calibration temperature is higher, add correction to average meter
      temperature for calculations.
Stack Temperature Sensor
 o
Was a pretest temperature correction used?            yes	no
      If yes, temperature correction 	°F  (within  1.5% in. °R over range)
Average stack temperature of compliance  test, T, 	 °R .
Temperature of reference thermometer or  solution 	 °R  (within 10% of T.)
Temperature of stack temperature  for recalibration	 °R
Difference between reference and  stack thermometers,  AT, 	 °R
Do values agree within 1.5%?* 	yes   	     no
      If yes, no correction necessary for calculations.
      If no,  calculation must be done twice—once with the recorded values and once with
      the  average  stack  temperature  corrected  to   correspond  to the   reference
      temperature differential  (AT.) .   Both final results must be  reported.

Barometer

Was the pretest field barometer correct?	yes  	no
Posttest comparison?* 	 in. Hg  (within  0.1 in. Hg)
Was recalibration required? 	yes  	no
      If yes, no correction necessary for calculations when  the  field barometer has  a
      lower readings;  if the mercury-in-glass reading is  lower, subtract the  difference
      from the field data readings  for the calculations.
                      Figure 5.1.   Posttest calibration checks.
O

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                      :                                         Section No.  3.19.5
                                                               Date September 3,  1992
                                                               Page 3

         2.    In boiling water for stack temperatures from 100 °c to  200  °C.
         3.    In a boiling  liquid with  the  boiling point  above 200  °C  for stack
               temperatures between 200 to 405 °C.  For stack temperatures above 405
               °C,  compare the  stack thermometer with  a thermocouple at a temperature
               within  10% of the average  stack temperature.   If the absolute values
               agree within  1.5%,   the  calibration is  considered  valid.    If  not,
               determine the  error  (AT.) to correct the average stack temperature.

5.1.3    Barometer—The field barometer should be  compared to a Hg-in-glass barometer.
If the readings agree within 5 mm (0.2 in.) Hg, the field readings  are acceptable; if
not, use the  lesser calibration value for the calculations.  If the field barometer
reads  lower  than the Hg-inglass barometer, the  field data  are  acceptable.   If the
Hg-in-glass barometer gives the lower  reading, use the difference in the two  readings
(the adjusted barometric value) in  the calculations.
5.2
Sample Preparation
         Field samples and reagent blanks should be'prepared concurrently, if possible.
Check  the  liquid  level  in each  container to  see whether  liquid was lost during
transport.  If a noticeable amount of leakage  occurred,  either void the sample or use
methods subject to the approval of the Administrator-to account for the losses.  Record
the findings of the liquid level check on the sample1 preparation data form, Figure 5.2,
or another suitable form.  Then follow the procedures below.
5.2.1    Containers Wo. 3 and
following procedures apply:
                     No. 4 (Filter and Filter Blank)—1£ a. filter; is used, the
               Place  the contents,  including the  filter,  of  Container  No. 3  in a
               separate,  properly  cleaned,  and  uniquely identified  250-mL beaker.
               Using  three rinses of approximately 10 mL of water, complete the sample
               transfer from the container.   Record the beaker number with the run
               number on  the sample preparation data form.
               Place  the contents  of  Container No.  4  in a  properly  cleaned 250-mL
               beaker.   Label it as the sample filter blank or  as another suitable
               name.   Use three  rinses of approximately 10 mL of water for the sample
               transfer.  Record the name on the  sample preparation data  form.
               Heat the beakers  in a laboratory hood on a steam bath until most of the
               liquid has evaporated.    Do  not take  to dryness.    Do  not use direct
               heating on a hot plate.  Record the completion  of the step on the sample
               preparation data  form.
               Add 20 mL  of  concentrated HN03 to each beaker,  cover  each beaker with a
               watch  glass,  and  heat on  a hot plate at 70 °C • for 2 h in  a laboratory
               hood.   Record completion of  this  step on the sample preparation data
               form.

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                                                              Section No. 3.19.5
                                                              Date September 3, 1992
                                                              Page 4
                            Sample Preparation Data Form

Date _  Plant Name _  Sampling Location

Sample Preparation Checks

      Sample Integrity Check:  Have containers leaked?

                  Container  1     _   4   _
                               1A  _   5   _
                               2   _   6   _
                               3
                                                      Run     Run    Run     Blank
                                                       123

                        Place a check to indicate completion
                        of step or record data as indicated.
Preparation of Filter Digest:  Container No. 3

Sample No. for each 250-mL beaker
Contents added to a glass 250-mL beaker?
Heated carefully to near dryness
      (not dryness) using a steam bath?
Volume of HNO3 added to beaker 25 mL?
Covered with watch glass?
Heated at 70 °C on hot plate  for 2 h?
How was temperature monitored?
Filtered through Whatman 40 paper ?
      Date
      Time
Rinsed beaker residue carefully through
      the filter?
Saved filtrate?

Preparation of Sample No. A.I:

Are Container No. 1 contents  <1000 mL?
      If so,  volume, mL
Are Container No. 1 contents  filtered through
      Whatman 40 paper?
Filter saved?
Filtrate added to mL glass volumetric flask?
Filter digest (above) added to flask with
      Container No. 1 filtrate?
Completion of Sample No. A.I?
      Date
      Time
 o
o
                     Figure 5.2.  Sample preparation data form.

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                                                               Section  No.  3.19.5
                                                               Date September  3,  1992
                                                               Page 5
                                                      Run     Run     Run    Blank
                                                       1  •     2    ••..-.  3
Preparation of Sample No. HCl A.2:

25 mL of  8N HC1 added to filter saved from
      preparation of Sample No. A.I?
How was HC1 added?
Digestion started, Time
      Date
Digestion ^completed, Time
      Date
HC1 digest dilution volume, mL

Preparation of Filter Blank;

Container 4 contents added to 250-mL beaker
Heated carefully to near dryness
      (not dryness) using a steam bath?   -^"n-
Volume of HN03 added to  beaker 25  mL?
Covered with watch glass?
Heated at 70 °C on hot plate for 2 h?
How was temperature monitored?

Preparation of Sample A.I Blank;

Are Container No. 5 contents diluted to same '
      volume as Container No. 1 contents?
Filtered  through Whatman 40 paper?
Filter saved?
Filtrate added to 1000-mL glass
      volumetric flask?
Filter blank (Container No. 4) digest (above)
      added to same volumetric flask?
Time of completion of Sample No. A.I

Preparation of Sample No. HCl A.2 Blank;

25 mL of  8N HCl added to filter saved from
      preparation of Sample No. A.I blank?
How was HCl added?
Time 24-h digestion started?
      Date
      Time
Time 24-h digestion completed?
      Date
      Time
HCl digest was diluted to 500 mL using glass
      volumetric flask?
                              Figure 5.2.   (Continued)

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                                                              Section No. 3.19 .5
                                                              Date September 3, 199
                                                              Page 6

         Note: The analysts should use gloves and safety glasses and should avoid skin
         contact and breathing the fumes from the HN03.
         5.    Remove  the  beaker  from the hot plate and filter the solution  from the
               digestion of the contents of Container No.  3 through a separate Whatman
               40 filter paper into a properly cleaned and identified (the same sample
               identification  number can  be used)  sample  container  using  a  vacuum
               filtering system.  Use three rinses of approximately 10 mL of water for
               the sample transfer.  The  filtration should be conducted in a laboratory
             •  hood.   Record the  completion of this step on the  sample  recovery data
               form.
         6.    Save the filtrate  for addition to the Container No. 1 filtrate,  as de-
               scribed in  Subsection  5.2.2.   Discard the  filter.
         7.    Filter the solution from the digestion of the  contents of Container No.
               4  (sample filter blank)  through Whatman 40 filter paper,  as described
               above in Step 5,  and save  the filtrate for addition  to the Container No.
               5 filtrate, as described  in  Section  5.2.2.  Discard the filter.

5.2.2    Container No. 1  (Impingers,  Probe,  and Filter Holder) and. If Applicable, 1A
(HCl Rinse)—The KMnO4  impinger solution and  rinse  and HCl  rinse  (if  applicable) are
prepared as follows:                            -*~

         Note: Because of  the hazardous  nature of the HNO3 and HCl solutions,  analysts
must wear gloves and safety glasses  and should avoid skin  contact and  breathing they
fumes from HN03 and HCl.  The HNCX, and KMnO4 solutions  should not come in contact wit*
oxidizable matter.
         KMnO, Impinqer Solution  and Sample Recovery Rinse
         1.    To remove the brown MnO2 precipitate, filter the contents of Container
               No. 1 through a Whatman 40 filter into a properly cleaned and identified
               1-L volumetric flask.  Use three rinses of approximately 10 mL of water
               for the sample transfer.
         2.    Save  the  filter  for  digestion  of  the  brown  MnO2  precipitate,  as
               described in steps 6 through 9 below, and  record the date and time the
               filtration  step was completed  on the sample preparation data  form.
         3.    Add the  sample  filtrate  from Container No.   3  produced  in Subsection
               5.2.1 above  to  the appropriate 1-L  volumetric  flask from Step 1, and
               dilute to volume with water.  If the combined  filtrates are greater than
               1000 mL, determine the volume to the nearest mL and record the volume
               on the sample preparation data form.  This volume will be used to make
               the  appropriate  corrections  for  blank  subtractions  and  emissions
               calculations.
         4.    Mix thoroughly.   The filtrate will be referred to as Analysis Sample No.
               A.I.
         5.    The Analysis Sample No.  A.I  must be analyzed for  Hg within 48 h after
               completion of the filtration step.  If the sample is not analyzed within
               this period, steps 1 through 4 must be repeated, the additional Whatman
               40 filter paper will be digested as  described below in steps  6 through
               9, and the digestion will be added to the  sample.
         Whatman 40  Filter and MnCs  Precipitate
         6.    Place  the   saved  filter,  which was used to  remove  the  brown  MnQf  ^
               precipitate, into a container of appropriate  size.  Submerge the  filte\>_y'
               with 25 mL of 8 N HCl and allow it and  the brown residue to digest for
               a minimum of 24  h at room  temperature.  Record the  date  and time  for the
               beginning of the digestion on  the  sample  preparation data  form.

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                                                               Section No.  3.19.5
                                                               Date September 3,  1952
                                                               Page 7
         Whatman 40 Filter. MnO, Precipitate,  and HC1 Rinse
         7.    Filter the  contents  of Container No.  1A,  HC1  rinse  (if applicable)
               through a Whatman  40 filter  into "a properly  cleaned and identified
               500-mL volumetric flask.  Use three  rinses  of  approximately 10 mL of
               water  for  the  sample  transfer.    Record  completion  on  the  sample
               preparation  data form.
         8.    Filter the digestion of the brown MnO2 precipitate and Whatman filter
               from Step 6 into the  500-mL volumetric  flask from Step 7.  Use three
               rinses of approximately  10 mL of water for the sample transfer.  Record
               the date and time of the  filtration on the sample preparation data fora.
         9.    Dilute to volume with water.   This  solution  will be  referred to as
               Analysis  Sample No.  HC1 A.2.   Save  the solution  for  Kg analysis as
               described in Subsection  5.3.4  below.   Discard the filters.

5.2.3    Containers No. 5  (Absorbing Solution Blank) and No.  6  (HC1 rinse blank)-Tne
procedures for preparing the blank solutions are described below:

Note: The same precautions  should  be  taken with the blank solutions as were taken with
the  sample  solutions.   The sample  blanks  have been  designed to allow easy blank
subtraction from the sample.  The volume of all solutions and the number of filters are
identical to the field samples.  Therefore,  the blank sample must be prepared at the
same time and in the  same manner as  the field samples.
         KMnO4 Reagent Blank Solution and Sample Recovery  Blank Rinse
         1.    Treat  Container  No.  5  (650 mL of blank absorbing  solution) the same as
               Container No.  1  (described in  steps  1 through 5 in Subsection 5.2.2).
         Filter Blank
         2.    Add the filter blank  filtrate  from Container No.  4  (completed in steps
               1  through 7  of  Subsection 5.2.1 above)  to the  1-L  volumetric flask
               (containing  Container No.  5   filtrate),  and dilute  to volume.   Mix
               thoroughly.
         3.    This solution will  be referred to as  Analysis Sample No.  A.I blank.
         4.    Analysis Sample  No. A.I  blank must be analyzed for Hg within 48 h after
               the completion of the filtration  step.

         Whatman 40 Filter and KMnO4 Reagent Blank Precipitate
         5.    Digest any brown precipitate remaining on the filter from the filtration
               of  Container  No.  5  by the  same procedure  described  in step  6 ir.
               Subsection  5.2.2 above.

         Whatman 40 Filter, KMnO4  Blank Precipitate, and Blank HCl Rinse
         6.    Filter the contents  of Container  No.  6 by the same  procedure described
               in  steps  7,  8,  and 9  in Subsection  5.2.2 and combine into the 500-nl
               volumetric   flask  with  the  filtrate  from  the  digested  KMnO< blar.k
               precipitate.   The  resulting  500-mL combined dilute  solution  will be
               referred to as Analysis  Sample No. HCl A.2 blank.  NOTE:  As  discussed ir.
               Subsection  5.3.4 below,  when analyzing  samples A.I blank and HCl A.2
               blank,  always begin with 10-mL aliquots;  this note applies  specifically
               to  blank  samples.
5.3
Analysis
         Precise  and accurate  analysis  requires  that  the  Hg  analysis  system  bs
calibrated properly,  which includes preparing calibration standards and field samples.

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                                                              Section No. 3 .19.5
                                                              Date September 3, 1992
                                                              Page 8

For  Method  101A,  spectrophotometer  calibration  is  conducted  in conjunction with
analyzing  the  field samples (and QA  samples).  This  section presents  the steps for
analyzing  the field samples and includes preparing sample and field blanks, as well as
describing how to quality control (QC) samples.  It discusses the relationship between
analyzing  the field samples and  preparing the calibration curve.

5.3.1    Instrument  Setup-Before use, clean  all  glassware,  both new and  used,  as
follows:   brush with soap and tap water,  liberally rinse with tap  water, soak for 1 h
in 50% HN03,  and then rinse with deionized distilled water.

         Flow Calibration—Assemble the aeration system as shown in
Figure 5.3.   Set the  outlet  pressure on the  aeration  gas cylinder regulator to a
minimum pressure of 500 mm Hg (10 parts per  square  inch  [psi]); use the flow metering
valve and  a  bubble  flow meter or wet-test meter to obtain a flow rate of 1.5 ± 0.1
L/min through the aeration cell.  After the  flow calibration is completed, remove the
bubble flow meter from the system.

         Optical Cell Heating System Calibration-Using a 25-mL graduated cylinder, add
25 mL of water to the bottle section of the  aeration cell.  Attach the bottle section
to the bubbler  section of the cell.  Connect  the fferation cell to  the optical cell and,
while  aerating  at  1.5 L/min,  determine  the  minimum variable transformer  setting
necessary  to prevent  condensation in  the  optical  cell and in  the  connecting tubing.
(This setting should not exceed  20 volts.)

         Wavelength Adjustment—Set  the spectrophotoraeter  wavelength  at 253.7 nm and
make certain that the optical cell is at the  minimum temperature needed to prevent
water condensation.

         Recorder Adjustment—The Hg response may be measured by either peak height or
peak area.  Peak height  determinations  may be performed manually by counting the
recorder paper divisions for a given peak from a best-drawn baseline.  The peak height
from the baseline also may  be measured  conveniently using a millimeter ruler.  Peak
area measurements are most conveniently accomplished electronically using an integrator
or similar device.   For peak height determinations, set the recorder scale  as follows:

Note: The  temperature of  the solution affects  the  rate  at  which elemental  Hg is
released from a solution and,  consequently,  it affects the shape  of the generated peak
as well  as the peak height.   Therefore,  to obtain reproducible  results using peak
height, bring all solutions to room temperature before use.
 o
O
o

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                                                              Section No. 3.19.5
                                                              Date September 3,  1992
                                                              Page 9
           NEEDLE VALVE FOR
             FLOW CONTROL
CYLINDER
                                   CELL
FLOW
METER
               EXIT ARM
                                              Hfr
                                                           TO HOOD
                                 TO VARIABLE TRANSFORMER
                        PTICAL CELL
                                                 MAGNETIC STIRRING BAR
                                    MAGNETIC STIRRER
                      Figure 5.3.   Schematic of aeration  system.

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                                                              Section No. 3 .19 .5
                                                              Date September 3, 195
                                                              Page 10

         1.    Place a  Teflon-coated stirring  bar  in  the  bottle.   Using  a  25-cL,
               graduated cylinder,  add 25 mL of  laboratory pure water to the aeration
               cell bottle.   Pipet 5.0 mL of the working Hg standard solution to the
               aeration cell.
         2.    Add 5 mL of the 4% KMn04 absorbing solution followed by 5 mL of 15% HNO:.
               and 5 mL of 5% KMn04 to the aeration cell  and mix well using a swirling
               motion.
         3.    Attach  the bottle to  the  aerator making sure that:  (1)  the  exit am
               stopcock is closed, and (2)  there  is no aeration gas flowing through the
               bubbler.
         4.    Through  the side arm, add 5 mL of sodium chloride hydroxylamine solution
               in 1-mL  increments until the solution is  colorless.
         5.    Through  the  side arm, add 5 mL of the  Tin  (II)  reducing agent to the
               aeration cell  bottle and immediately  stopper  the side arm.
         6.    Stir the solution for 15 s  and  turn on  the recorder or  integrator.
         7.    Open the aeration cell exit  arm stopcock  and  initiate the gas  flow.
         8.    Determine the maximum height (absorbance) of the standard and set this
               value to read  90% of the recorder full  scale.

5.3.2    Analytical Calibration Curve-After setting the recorder scale (Section 5.3.1! ,
the  calibration is performed.    To separate aeration  cell bottles,  add 25  mL  cf
laboratory pure water.   Then add 0.0-, 1.0-, 2.0-, '3.0-, 4.0-, and 5.0-mL aliquots cf.
the working standard solution using Class A volumetric pipets. This corresponds to C,
200, 400, 600, 800, and 1,000 ng of  Hg,  respectively.  Proceed with the calibration,
following  steps  2  through  7 of  Section  5.3.1, Recorder  Adjustment.   Analyze the
calibration standards  by measuring the  lowest  to the highest standard.   Be sure tc
allow the  recorder pen to  return fully to the  baseline before the next standard is
analyzed.  This step is particularly critical with peak area measurements.  Repeat this
procedure on  each aliquot  size until two consecutive peaks agree within  3% of the
average.
         Between  sample analyses,  place  the  aerator  section  into a  600-mL beaker
containing approximately 400 mL of water.   Rinse the bottle section of the aeration
cell with a stream of  water to remove all traces of  the  reagents from the previous
sample.  These steps are necessary to remove all traces  of the reducing agent between
samples to prevent the loss of  Hg before  aeration.   It will be necessary, however, -z
wash the  aeration cell  parts with concentrated HC1 if  any of  the  following conditions
occur: (I) a white film appears on any  inside surface of  the aeration cell;  (2) the
calibration  curve  changes  suddenly;  or  (3)   the  replicate samples  do  not yield
reproducible results.
                                                                                -   o

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                                                               Section No.  3.19.5
                                                               Date September 3,  1992
                                                               Page 11

         Recorder or integrator responses should be documented on the  analytical  data
 form for Calibraxon Standards (Figure 5.4) .  Subtract the average peak  height  (or  peak
 area)  of  the measurement   blank  (0.0-mL aliquot) -which  should be less than 2% of
 recorder full scale— from the averaged peak heights of the  1.0-,  2.0-,  3.0-, 4. 0-, and
 5.0-mL aliquot standards.  If the  blank absorbance  is greater than 2% of full-scale,
 the  probable cause is  Hg contamination  of a  reagent  or carry-over of Hg from a
 previous sample.  Plot the corrected peak height of  each standard solution versus the
 corresponding total Hg mass  in the aeration cell  (in ng) .
         Calculating the measured  standard Hg mass  (P) may be performed in two ways:
 a linear regression program provided by a hand calculator  (or other computing device)
 or the manual least squares method described below:        .   . ..

         P  =  (S) (Y)                                                    Equation 5-1

 where :

         Y  =  Peak height or integrator response, mm or counts.

         S  =  Response factor,  ng/mm or ng/counts  (from Equation  5-2) .
                                               -*
 and                                               >                         '  ""

               *iy i +X2y2-Hx3y3 +x4y 4 +xsy 5+x6y 6
         S  =  -                            Equation 5-2
where :

         x  =  Standard mass value,' ng.

         Complete the analytical data form for analyzing calibration standards  (Figure
5.4) for each standard.  Calculate the  deviation of each standard measurement average
from the expected value  (standard mass value),  x.  If the  percent deviation from the
expected value is greater than 5%  for  any standard measurement, the calibration must
be repeated.

5.3.3    QC  Operations— The  quality of the  analytical results  can  be  assessed by
analyzing a variety of standard reference solutions  (SRMs) of known high accuracy, such
as those available  from the National  Institute  Standards  and Technology (NIST) and
other government agencies.  Standard solutions prepared by commercial suppliers that
meet NIST traceability criteria are also useful.'- If these solutions are not available,
the  analysis  of laboratory-prepared standard solutions may  be used from  a  source
(supplier) other than the source of the calibration standards.  These solutions will
be known as QC solutions. For example, if  the calibration  standards were prepared by
dilutions of a  100  mg Hg/mL solution  from  supplier  A (or  from an in-house prepared
solution  from  the pure  mercury salt), then a  QC  solution  might be  prepared from
dilutions of one of the  following:
         1.   An NIST Hg solution or other SRM.

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                                                              Section No. 3 .19.5
                                                              Date September 3, 1952
                                                              Page 12
                                                                             o
Plant Location
Date Analyst

Standard
Identifier
Std 1
Std 2
Std 3
Std 4
Std 5
Std 6
Standard
mass
(x)
(ng Hg)
0
200
400
|_
600
800
1000
Integrator Response
Peak Height or Area
(y) , (mm)
1






2







,
Avg




1
..rl
1
1 ''
Measured
Standard
mass
(P)
(ng Hg)


Deviation
(%)

1
!
I
I




Equation  for  Linear Calibration Curve, Average  Response as a  function  of standard
concentration.
                                                                             O
y  =  mx + b = (
                              )x + (
where:
         y  =  Instrument curve slope mm or area count =
                                            ng Hg
         x  =  Standard concentration (ng Hg) = 	

         b  =  I = Intercept term (mm or area count) =

Measured Standard Concentration (P)
Equation 1


Equation 2


Equation 3

Equation 4
         P(ng Hg)   =  Average Instrument Response (y) - Intercept (I)
                                   Calibration Curve Slope
                                                ng Hg
                                                                 Ecuatior. 3
Deviation
         Deviation  (%)     =  P (nq Hq) - x (no Hq) x 100%
                                     x (ng Hg)
         Deviation    =  (
                                )  x 100% =
                                                                          Ecuatior.  €
           O
      Figure 5.4.  Analytical data form for analysis of calibration standards.

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                                                              Section No. 3.19.5
                                                              Date September 3, 1992
                                                              Page 13

         2.   A commercial QC solution that has been tested against an NIST solution
               (or equivalent) by manufacturer A.
         3.   A 1,000-mg Hg/mL solution from manufacturer B.
         Record analytical  data for QC samples on Figure 5.5.  QC solutions may be used
for a variety of analytical accuracy assessments.   These include  three check samples
(Check Sample A,  B,  and C):
         A.   Checks  of the accuracy of the  calibration  operations, ChecJc  Sample
              A—When analyzed immediately following the calibration,  the measured QC
              sample value must be within 5% of the expected value described in this
              section,  or  the  calibration must be  repeated.   These QC samples  are
              known as  Initial Calibration Verification  (ICVs) Check samples.
         B.   Checks of the drift of the calibration, Check Sample B-For any of a wide
              variety  of  conditions  that  may  be  related  to  instrument warmup  or
              instrument component  deterioration, :the repeated analysis of a  given
              sample or standard will vary over time.  To ensure thit the analysis is
              "in control,"  a  QC solution is measured at least  every  five  samples.
              If the  average measured value of the QC solution has  changed by more
              than  10%  from the expected value, the  causes must be  identified  and
              corrected.  The calibration is then repeated,  and all samples  analyzed
              since the last successful "drift"_rQC sample analysis must be  repeated..
              This  "drift" QC  sample is  known  as a CCV sample.   It  is worth  noting
              that the CCV need not be a "standard" type solution; any Hg-containing
              solution may be used for the CCV,  provided the Hg level in the aeration
              cell  is between  200  and 1,000 ng.  Again, the measured value of this
              solution must  not vary more than  10%  from the expected value.
         C.   Measuring spike recovery check sample, Check Sample C—Spiking a digested
              sample  (a prepared sample)  with a standard solution provides a means of
              assessing Hg recovery  associated with the  measurement  process  (sample
              matrix  effect).   The steps below must be followed  to  determine  spike
              recovery:
              a.  After completing all sample preparation steps in Subsections 5.2.1
                  and 5.2.2, spike a 10-mL aliquot  of  Analysis Sample No. A.I with 10
                  mL  of spiking solution containing a  similar concentration of Hg, or
                  with 10  mL of a spike at  least 10 tiroes greater than the detection
                  limit, whichever is greater.
              b.  Spike a  10-mL aliquot of  Analysis Sample No. HC1 A.2 with 10 mL of
                  spiking  solution containing a similar concentration of Hg  as the
                  field sample,  or  a  spike  at  least  10  times  greater than  the
                  detection  limit,  whichever is greater.
              c.  After all  samples  are analyzed, subtract the results of the spiked
                  and unspiked samples.  If this spike is not within  15% of the expe-
                  cted value, then the Hg response may be owing to matrix effects. If
                  so,  all  sample digests must  be analyzed by the method of standard
                  additions  (MSA).
                                                                    f\
                                                                  i
                                                                  v:

-------
Date samples
Plant
received Date samples analyzed
Run number (s)
Location Analyst
Calibration factor (S) Intercept (I), if applicable

QC
Sample
Number


Analysis
Number

Instrument
Response
(mm)

Deviation of replicate measurements, (%)
Mass of QC sample
without intercept
(ng Hg)
Mass of QC sample
with intercept
Mean
Instrument
Response
(mm)

Mean
Instrument
Response (Mass
Percent Blank Dilution QC
Deviation Corrected Factor Sample
(ng Hg) (y) (F) (ng Hg)

(A, - A2)
x 100
A, -f A,
2
- ( ) - ( ) 100 =
( ) + ( )
2
v o to
$i 01 (f)
- S x v x F 0 Z ~
— o-A.yJvr (liOfT
= 	 _ „,- X X ......... 	 = f-1 rn O
rr 2
S o
= S (y - I) F §•'
i - \ - V. w
  (ng  Hg)
O
Figure 5.5.  Analytical data form for analysis of QC samples.
                                                                                                        ID
                                                                                                        K)
                                                                                   O

-------
                                                                     Section No.  3.19.5
                                                                     Date September 3, 1992
                                                                     Page 15

               Operations involving the use of QC samples are described in more detail below.
      Note that spikes always must be measured using the linear portion of the calibration
      curve (as with actual samples) .  QC samples with Hg values exceeding the linear portion
      of  the  calibration curve  must be  diluted and  reanalyzed  according to  the  sample
      analysis procedure (Subsection 5.4.3).

               Preparing  the ICV Solutions—If  the source  of the  ICV  is  a  commercial
      1,000-mg/mL stock solution,  it must be diluted according to the  procedure described in
      Subsection 1.5.3 for intermediate and working standard solutions.

               Measuring the ICV Solution-Analyze a  2- to 5-mL aliquot (i.e., 200-500 ng Hg)
      of the ICV working standard solution (some mid-point aliquot).   Duplicate measurements
      should agree within 3%  of the average.  If not, determine the cause for error (consult
      the  laboratory  supervisor  if  necessary),  correct the problem,  and  recalibrate the
      analysis system.  Repeat as necessary.   If the QC solution  source is not a 1,000-mg
      Hg/mL stock solution,  prepare  the  intermediate QC solution  (QC working solution)  as
      follows:
               1.    Pour  about  15 mL of the solution  into a  clean beaker. NOTE: To avoid
                    contamination,  do  not pipet  directly  from the bottle.
               2.    Pipet  (using a  glass  pipet of at  least 5-mL volume) an  appropriate
                    aliquot  into a suitable clean glass volumetric flask, according to Table
                    5.2.  Pipet 2 mL of the QC working solution for measurement. Use Table
                    5.2 to determine the  expected values  for  the QC  sample (ICV) .

               Preparing and Measuring the Initial Blank Verification  (IBV) and Continuing
      Blank Verification (CBV)-Vlith  the conventional measurement system, these verifications
"''''    may be performed merely by  adding 50 mL of water, hydroxylamine sulfate solution, and
      stannous chloride as described in Subsection 5.3.2.

               Preparing and Measuring Spiked  Sample,  Check Sample  C—To determine whether
      there are sample matrix effects during  the  measurement, one  sample digest must  be
      analyzed in the presence of added Hg.  The added  (spiked) Hg recovery must be within
      85-115%, or the MSA must be employed for each sample and blank digest.

-------
                                       TABLE 5.2  PREPARATION OF QC SOLUTIONS
Certitied value of
QC source solution
(ng Hg/mL)
<1
1-5
5-20
20-100
Aliquot of QC
source solution
for dilution, (mL)
A

5
5
5
Dilution
Volume, mL
vd
	
100
250
1000
QC working
solution
concentration
using Eq. 1
(ng Hg/mL)
cu,




Volume of
working solution
taken for
analysis, (mL)
«
2
2
2
2
Expected
value, (n
using Eq.
M




Hg
g)
2




where:
where:
Cws


cecd


vd


A


M.
         M
          'Hg
        £std

        Vd
                     x_A
                 Concentration of  QC  "working"  solution (WSQC), ng Hg/mL.


                 Concentration in  ng  Hg/mL of QC source solution ' (QC).


                 Dilution volume in mL.


                 Aliquot of QC source solution added to volumetric flask  in mL.
                 Cw.  x VB.
        Expected ng Hg  in aeration flask.


        Aliquot of Cw, taken for measurement, mL.
Equation 1
                                                                                                          Equation 2
     >o o en
     P> P> (D
     iq rr o
     (K n> rr
         H-
     M Cfl 0
     0*3

       rt Z
       n o
       O
                                                  o
     O"

-------
below:
                                                     Section 3.19.5
                                                     Date April 3, 1992
                                                     Page 17

The procedure used to determine the existence of matrix effects is described

1.   Analyze an aliquot of the sample and record the sample aliquot size used
      (see Subsection  5.4.3).
2.   Calculate the Hg content in ng of the sample aliquot.
3.   Determine a  working standard aliquot size that equals or exceeds the
     sample response  from Step 2.
4.   Add the  value  determined from Step 3 to an additional sample  aliquot
     identical to that used in Step 1.
5.   Analyze this spiked sample and record the response.
6.   The spike recovery is calculated as follows:
         % Recovery
              =  C spiked sample -
                         C spike
C sample x 100
Equation 5-3
where;
         C spiked sample

         C sample

         C spike
                    =  Measured Hg  in  spiked sample, mg.

                    =  Measured Hg  in -onspiked sample, mg.

                    =  Hg added to  sample, mg.
         Note: To ensure the validity of the  spike measurement, it is imperative that
the measurement result fall within the range of the calibration.

         Method of Standard Addition Analysis—If the recovery result obtained from the
section above on the measurement of  spiked samples  falls  outside  the 85-115% range,
then the MSA must be employed for all sample digest measurements.   This procedure is
described below:
         1.   Repeat steps 1 and 2 of spiked sample measurement above to determine the
              level of Hg  in the sample (designated S0),r  ;
         2.   To a second,  identical sample aliquot, add a working  standard volume
              that  contains a  Hg level  that is  approximately 50% of  the  sample Hg
              level.  Refer to this spiked sample as Slf and record the exact aliquot
              volume of sample and working standard.used.
         3.   Analyze spiked sample  (Sj) .
         4.   To another,  identical  sample aliquot, add  a  working  standard aliquot
              that  contains an Hg level that is approximately equal  to that of the
              sample.  Refer to this  spiked sample as S2, and record the exact aliquot
              volume of sample and working standard used.
         5.   Analyze the  spiked sample (S2)  .
         6.   To another,  identical  sample aliquot, add  a  working  standard aliquot
              that  contains  an Hg  level that is  approximately 1.5 times that at the
              sample.  Refer to this  spiked sample as S3, and record the exact aliquot
              volume of sample and working standard used.
         7.   Analyze the  spiked sample (S3)  .
         8.   The  peak  intensity of  each  solution is determined  and plotted on the
              vertical axis of  a graph.   The concentrations of  the  known standards, are
              plotted on the horizontal axis.  When the resulting line  is extrapolated
              back  to zero absorbance,  the point of interception  of the abscissa is
              the  concentration  of the unknown.   The  abscissa on the  left of the

-------
                                                    Section 3.19
                                                    Date April 3,
                                                    Page 18
1992
o
      ordinate is scaled the same as  on  the  right side, but in the opposite
      direction from the ordinate.  An example is shown in  Figure 5.6.

u
c
ca
&
i-i
0
c/1
A
<
Zero
Absorb

Concen'
of Sa
ance s^[
/




1
f
_-
\ \
	 «,

r i


i Mass (ng)
Addition 0 Addn 1 Addn 2 Addn 3
-ration No addition50* Qf 100% of 150X of
mple Expected Expected Expected
Amount Amount Amount
                                                                          O
               STANDARD ADDITION  PLOT
   Figure 5.6. Method of standard additions for field samples.

To perform a valid MSA analysis, three criteria must be met:
1.   The MSA standard curve must be linear using  the criteria in Subsection
     5.3.2.
2.   The spiking level of Hg  must be at least 50% of  Hg in the  sample.
3.   The  spiking level  must  be at  least 10  times  the  detection  lirr.it
      (approximately 20 ng).
                                                                         O

-------
                                                               Section  3.19.5
                                                               Data April  3,  1992
                                                               Page 19

5.3.4    Field Sample Analysis-Repeat the procedure used to establish the calibration
curve with an appropriately sized aliquot (1 to 5 mL) of the diluted sample until" two
consecutive peak heights agree as follows:

         Hg mass, ng                      Limits (% deviation  from average)

            <5                                      50
           5-15                                     15
          15-100     ;                               5
           >100                                      3

      /  An aliquot peak maximum (except  the 5-mL aliquot) must be  greater than 10% of
the recorder full scale.   If  the peak maximum of a 1-mL aliquot is off scale on the
recorder, further dilute the original source sample to bring the Hg concentration into
the calibration range of the  spectrophotometer.
         Run  a CBV and  a CCV  at  least after  every  five  samples  to  check  the
spectrophotometer calibration drift; recalibrate as necessary  (see Subsection 5.3.3).
It is recommended  that at least one sample  from 'each stack test be checked by the
method of standard additions  to confirm  that matrix effects have not  interfered with
the analysis (see Subsection 5.3.3).  Record alKriata for field sample analysis on.the
Method 101A field analysis data form, Figure 5.7, >or similar form.           •    \

         Analysis Samples No.  A.I and HCl A.2—After sample preparation of each sample
run,  two sample fractions  must be analyzed for Hg  to determine the total  ng of Hg.
Analysis Sample No. A.I is the filtrate of the KMnO< absorbing solution and rinse and
the digestate of the glass fiber filter,  if applicable.   Analysis  Sample No. A.I will
be 1,000 mL  or more,  measured to within 1  mL.   Analysis Sample ,,Nor.  HCl  A.2 is f the
digestate of  residue  and; Whatman  40 filter  paper and HCl  rinse,  if  applicable.
Analysis Sample No. HCl  A.2 will be  500 mL.  A recommended sequence of  analysis is
presented in Table 5.3.;

         Analysis Samples  No.  A.I Blank  and HCl A.2 Blank-Each test  series requires
that a sample blank be taken.   The sample blank is prepared in the same manner as the
field samples.  The analysis  of the  sample blank will have the same two 'fractions as
each field sample.   The blank  will be analyzed at the same time and in the same manner
as the  field samples,  with the exception  that a  10-mL aliquot  shall be  used for
analysis.  A recommended sequence of analysis is presented in Table 5.3.

         Container No. 2 (Silica Gel)4-Weigh the spent  silica  gel  (or silica  gel plus
impinger) to the nearest  0.5  g using a balance.  (This step may be conducted in the
field.)

-------
Date samples received
                        Date samples  analyzed
Plant Run number (s)
Location Analyst
Calibration factor (S) Intercept (I), if applicable




Field




Sample (Analysis
Number
,

Number




Instrument
Response
(mm)



Mean
Instrument
Response
(mm)

(A,
Deviation of replicate measurements. (%) =
A,

_ _£_
(




Percent
Deviation
(ng Hg)

.
Mean
Instrument
Response
Blank
Corrected
(y)





JMass
Dilution
Factor
(F)

Field
Sample
(ng Hg)

- A2)
x .100
+ A,
2
) - ( ) 100 =
) 4 ( )
                                                                    2
Mass of QC  sample

without intercept

          (ng Hg)



Mass of QC  sample

with intercept

          (ng Hg)
                         =  S x y x F
                                                     x
        O
                         =  S (y - I) F
Figure 5.7. Analytical  data form far analysis of  field  samples.
•ti a tn
pi fu ID
id rr n
eo (o rt
    H-
to > o
0-0 3
                                                                                                                   10

                                                                                                                   VO

                                                                                                                   (O
                                                                                      O

-------
                                                               Section  3.19.5
                                                               Date April  3, 1992
                                                               Page 21
                     TABLE  5.3  RECOMMENDED ANALYTICAL  SEQUENCE"
Sequence No.
1
2
3
4
5
6
7
8

9
10
J) "
12
13
14
15
16
17
18
19
20
Sample ID
IBV
repeat
ICV
repeat
ccvb
repeat
A.I blank
repeat

HC1, A. 2 blank
repeat
A.I, Run 1
repeat
A.I Spike, Run le
repeat
HC1 A. 2 Run ,lc „,
repeat*3
CCV
repeat
CBV
repeat
Sequence No.
21
22
23
24
25
26
27
28 \
\
29
30
31
32
33
34 ^
' ::" 35 ~; . -,





Sample ID
HC1 A. 2, Run 1 spike
repeat
A.I, Run 2
repeat
HC1 A. 2, Run 2 '
repeat
A.I, Run 3
repeat

HC1 A. 2, Run 3
repeat
CCV
repeat
CBV
repeat
Repeat Calibration"1 '





"Assuming a valid calibration has been performed.
blf different-than ICV.                  ,t, ,
^Any A.I spike from runs 1, 2, or 3.      ,-.-
    this point, if the recovery is  85 to 115%, proceed  to Step  26;  if
  ,ot, all  samples must  be  run /using MSA (Subsection 5.3.3).

-------
                                                              Section 3 .19 . 5
                                                              Date April  3,  1992
                                                              Page 22

5.4      Alternate Analytical Apparatus

         Alternative systems  are allowable as long as they meet the following criteria:

5.4.1    Measurement Technique—The system  is  based on cold vapor atomic absorption
techniques.

5.4.2    Analyte Recovery—Eighty-five-115% of the  spike  is  recovered when an aliquot
of a source sample is spiked with a known concentration  of  Hg  (II) compound.

5.4.3    Calibration Curve—A  linear calibration curve is generated and two consecutive
standards of the same aliquot  size and concentration agree within the following limits.

         Hg mass,  ng/mL                  Limits (% deviation from average)

           10                                      3

5.4.4    Sensitivity—The system is capable of detecting 0.2 ng Hg/mL for flow-injection
systems or 20 ng  Hg for batch systems.
                                                                                   o
                                                                                 •O
                                                                                 i--u«^>—<
         An example of a flow-injection analytical system is  depicted  in  Figure 1
Note that these systems inject samples in a semicontinuous manner;  consequently, the
solution concentration is monitored, not the total Hg in the entire sample.  Therefore,
the total Hg in a given sample digest is calculated as follows:

         MHa   =  CHg x V                                                Equation 5-4

where:

         MHg   =  Total mg  Hg in each sample digest from Section  5.2.

         CHg   =  Measured  concentration in mg Hg/mL.

         V    =  Total volume in milliliters of the sample digest.

         These calculations are shown in Section 3.19.6.

5.4.5    Data Quality Assessment for Alternate Analytical Systems-QC solutions used to
determine the accuracy of  the calibration may be measured directly without performing
the calculations described in Subsection 5.3.3.  This procedure, of course,  is based
on the  assumption  that the  sample concentration  value does  not exceed  that  of the
highest calibration standard, thereby requiring a dilution.
                                                                                  O

-------
 follows:
                                                     Section 3.19.5
                                                     Date April  3, 1992
                                                     Page 23

Determining  matrix effects  on the  measurement recovery  is performed  as


1.    Determine  the Hg  concentration  in  the  sample digest.
2.    Remove  two  10-mL aliquots  of  the  digest and place  in clean 20-mL
      beakers.
3.    To  one aliquot,  add 1  mL  of  distilled  deionized water  and  mix  by
      swirling the beaker  (S0) . —   -
4.    To the  other aliquot, add 1 mL of a standard that is 10 to 20 times the
      solution concentration of the sample;  mix  the beaker contents (S^ .
5.    Measure both solutions for Hg content.
6.    The  recovery of the  added spike  is  as  follows:
         % Recovery
                          Ms, - Mso
                             X 100
Equation 5-5
where:
         MSO
              =  mg Hg in spiked sampler
                                         \
              =  mg Hg/mL in St x 11 mL.

              =  mg Hg in sample spiked with water.

              =  mg Hg/mL (of spiking solution)  x 1  mL.
         The recovery should'be between 85-115%.  Otherwise, the method of additions
must be employed for each sample of the sample run.          --

         Method of Additions—In this method, equal volumes of sample are added to a DI
water blank  and to three standards  containing different known amounts  of  the test
element.  The volume of the blank and the standards  must  be  the same.  The absorbance
(peak height,  counts,  etc.)  of each solution  is determined and  then plotted on the
vertical axis of a graph.  The  concentration of the known standards are plotted on the
horizontal axis.  When  the  resulting  line is  extracted back to zero absorbance, the
point of  interception  of  the abscissa  is  the concentration  of  the unknown.   The
abscissa on the left of the ordinate is scaled the  same  as  on the right side, but in
the opposite direction  from the ordinate.  An example is shown in figure 5.6. .......
5.5
Posttest Checklist
         Posttest  checklists  for QC  sample  analysis and  field  sample  analysis are
presented in figures 5.8 and 5.9.                                           .

-------
                                                              Section 3.19.5
                                                              Date April 3, 1992
                                                              Page 24
  o
                            QC Sample Analysis Checklist

 Date 	  Plant Name 	  Sampling Location

 Calibration Standards and Matrix Checks

      Mercury Stock Solution, 1 rag Hg/mL:

      Prepared in-house'?  (Y/N)
      Source of mercury  (II) chloride
      Commercial stock solution?  (Y/N)
      Source              	    	
      Intermediate Mercury Standard Solution, 10 mg/mL:

      Date prepared 	
      Used glass pipet?  (Y/N) 	
      Source and grade of HNO3 	
      Working Mercury Standard Solution, 200 ng Hg/mL:

      Prepared today? (Y/N) 	
      Used glass pipet?  (Y/N) 	

      Calibration Standards:

                mL of working standards            volume  of volumetric  flask,  mL
            #1  	           	
            #2  	           	
            #3	           	
            #4  	           	
            #5  	                •	
            #6  	           	
            #7  	           	

Instrumentation:
      Spectrophotometer  type 	
 O
Moisture Removal System:
      Optical cell heating system? 	  Calibrated?
      Moisture trap used? 	  What type?

Data Recording System:
      Recorder 	  Integrator 	  Other
      Describe       	  	
      Peak height 	  Peak area
O
                           Figure 5.8.  QC sample analysis.

-------
                                                               Section 3.19.5
                                                               Date April 3, 1992
                                                               Page 25
Cold Vapor Generation System:
      Standard batch system?
      Alternate system? 	
      Describe alternate system?
      Aeration gas                ....  Aeration gas flow
      Gas cylinder? 	.      Peristaltic pump?
Standardization:
      Glass pipets used? _
mL of                .  Standard value*			 ...	   ?.••*:;•?. .»•  •; .
working standard  ....   -*(hg) '    •"••"•'           Reading 1 ;':    Reading  2     %Difference
"If using an alternate system that uses flow injection this value may be expressed as
concentration, e.g., |ig/L, ng/L,  etc.

Calibration coefficient	-  -
Offset at origin (measured response of calibration blank)           ng or % of scale.

Initial Calibration Verification  (ICV) ;           "' '
QC check sample source                                                   	
Certified or expected concentration                                      	
Measured concentration                                                   	
% Difference                           ''"'         •                           .;'	
Initial Calibration Blank Verification (IBV);
Measured value
Below detection limit?

Matrix Interference Check:
Method of additions performed  for  one test site sample?
Spike added
Spike recovered

% recovery = Spiked sample value - unspiked sample value =
                           spike value
                               Figure 5.8.  (Continued)

-------
                                                               Section  3.19.5
                                                               Date April  3,  1992
                                                               Page 26
o
If the recovery was outside of 85-115%,  were samples  run using the method of standard
      additions? 	
      Describe 	..

Continuing Calibration Verification (CCV) - Check sample of  standard to be reanalyzed
      after every five samples:
Standard used  (source)	.
Expected value/unit                                  	
Was measured value/unit always within 10% of expected value? 	

Final Standardization:

      Glass pipets used? 	

mL of                  Standard value"
working standard       (ng)                  Reading  1      Reading 2    %Difference
                                                                                  O
"Alternate analytical  systems may express Hg value as a concentration  (e.g., mg/L Hg).

Calibration coefficient 	

Offset at origin 	ng or % of scale.
                               Figure 5.8.  (Continued)
                                                                                   O

-------
                                                               Section 3.19.5
                                                               Date April 3,  1992
                                                               Page 27

                              Sample Analysis Checklist           " ~"  '

Date •            Time  ._      Operator        •••     Observer _______^___

                                   Sample Analysis

Were all sample digests analyzed within 48  h of preparation? _____( Y/N)

Were 10 mL of samples A.I blank and  HC1 A. 2 blank used as a minimum?
_ (Y/N)

Were duplicate measurements performed as a  minimum for all blank and sample digests?
Did duplicate measurements meet the "percent difference" criteria outlined in Table 5.2
_ (Y/N)

Was  the largest  possible aliquot  (20 mL)  used when a  measurement was  below  the
detection limit? _ (Y/N)

If a sample measurement exceeded the highest calibration standard, were appropriately
smaller aliquots always taken to ensure that results fell within the calibration range?
_ (Y/N)

If  1-mL aliquots taken  for measurement  still  were  off scale, were sample  digests
diluted so that results were  within  the linear  range of the standards?       (Y/N)

What volumetric  glassware  (pipets)  was used to add sample digests  to the aeration
flasks? _ (mL)                             '

What volumetric glassware  (pipets/ flasks) was used to dilute sample digests?  _______
__ (if necessary)                                                               ,

If the calibration check samples differed by greater  than  10% of the expected  values,
was the system recalibrated?       (Y/N)

Were CBV and CCV samples analyzed  after ever five samples? _ (Y/N)

Were all samples run after the previously CBV and CCV sample analyses?  . --
_ (Y/N) '

Was the full standardization  performed at the end of the sample analysis? _ (Y/N)
                 Figure 5.9. Method 101A sample analysis checklist.
                                                                        <

-------
                                                               Section  3.19 .5
                                                               Date  April  3,  1992
                                                               Page  28
o
                   TABLE 5.1  ACTIVITY MATRIX FOR SAMPLE ANALYSIS




Characteristic
Sample

preparation



All




calibrations






1
1
(Acceptance limits
1
| Samples and
(blanks prepared
I under same
| conditions
1
1
|(1) Reagents and
(volumes used
(during
(measurement of
| samples and

Frequency & method
of measurement
	




Dilute samples so
that matrix
concentrations are
are identical to
original sample
(Action if
| requirements
| are not met
I
(Adjust
(dilutions, if
(possible;
(otherwise report
(to Administrator
1
| Reanalyze
| samples
j
1
1
(standards are (digest |




| identical
1
| (2) Perform
.— • ' '
•-
Prepare fresh
| 6 -point (daily














(calibration curve
I including
(calibration blank
1
I (3) Calibration
(coefficient
(better than 0.999
'



Each calibration
point is the
average of
( (duplicate
1
1
1
| Prepare fresh
(daily
1 /
1 (
1

(Repeat
(calibration
1
1
| (measurements |
1 1
Calibration
Verification
Check Samples
(ICV)

Calibration
Blanks

(Analysis within (Analyze after
| 5% of expected or
I certified value
1
1
every calibration


(Must be below (Analyze after
(detection limit
Verification I
(IBV)



Continuing
Calibration
Verification
Sample


(CCV)


1
I
I
every
calibration


(Must be within (Analyze after
J10% of expected
(value
1
|
1
every 5th sample




(Ensure quality
(of check sample
| or repeat
| calibration
(check for
(potential
(contamination
(and repeat
| calibration
1
| Repeat
| calibration
(and repeat all
(samples since
| last successful .,
|CCV analysis v __ {
                                                                                    O
                                                                                    o
(Continued)

-------
                                                              Section 3.19.5
                                                              Date April 3, 1992
                                                              Page 29
TABLE 5.1  (Continued)
Characteristic
Continuing
Blank
Verification
(CSV)
Matrix check
sample
Duplicate
measurements
Data recording
Acceptance limits
Must be below
detection limit
Recovery of
sample digest
spike 85-115%
See Subsec.
5.3.2
All pertinent
data recorded
on figs. 5.1, 5.2
Frequency & method
of measurement
Analyze after
every 5th sample
One sample digest
from every stack
test is spiked at
a level at least
equal to sample
digest
conccntrat ion
All standard and
sample analyses
Visually check
(Action if
| requirements
(are not met
1
1 Repeat
(calibration
land repeat all
(samples since
I last successful
|CBV analysis
!
(Analyze all
(samples using
|the method of
| standard
(additions
1
1
(Repeat until
| agreement is
| achieved
1
(Supply missing
(data
1

-------
o
o
o

-------
                                                              Section No.  3.19.6
                                                              Date September 3,  1992
                                                              Page 1
6.0
         CALCULATIONS
         Calculation errors resulting from procedural  or mathematical mistakes can be
a part of total system error.   Therefore,  it is recommended that each set of calcula-
tions be repeated or spotchecked, preferably by a team member other than the one who
performed the original calculations.  If a difference greater than typical round-off
error is detected,  the  calculations should be checked step-by-step until the source of
error is found and corrected.
         Calculations should be carried out to at least one extra decimal figure beyond
that of the  acquired data  and should be rounded off  after final  calculation to two
significant digits for  each run or sample.  All rounding of numbers should be performed
in accordance with the ASTM 380-76 procedures.
         A computer program is advantageous  in reducing calculation errors.   If a
program is used,  the  original data  entered should be included in the  printout for
review.  If differences are observed, a new computer run should be made.  A computer
program also is useful in maintaining a standardized format for reporting results.  The
data shown will allow auditing the calculations.
         Table  6.1  at the  end  of  this  section  summarizes   the  QA activities  for
calculations.                                  -*~  .
         In the next section,   nomenclature  and equations  have been divided into two
groups.  The first group (Section 3.19.6.1 to 3.19.6.4) deals with sampling calcula-
tions.  The  second  group (Section 3.19.6.5 to 3.19.6.13) deals with analytical and
emissions calculations.
6.1
         Sampling Nomenclature from Method 5
         An


         Bw,


         I


         L.
         L,
         R
                   Cross-sectional  area of nozzle, m2 (ft2).

                   Water  vapor in the gas stream, proportion by volume.

                   Percent  of  isokinetic sampling.

                   Maximum  acceptable leakage rate for either a pretest leak check or
                   for  a  leak  check  following  a component change, equal  to 0.00057
                   mVmin (0.02 cfm) or  4% of the average sampling rate,  whichever is
                   less.

                   Individual  leakage rate observed during the leak  check conducted
                   prior  to the "ith"  component change (i = 1, 2, 3...n), mVrnin  (cfm).

                   Leakage  rate observed during the posttest leak  check, mVmin  (cfm).

                   Molecular weight of water,  18.0 g/g-mole  (18.0 Ib/lbmole) .

                   Barometric  pressure at the  sampling  site, mm Hg (in.  Hg).

                   Absolute stack gas pressure,  mm Hg  (in.  Hg).
                                                                                 t,
                   Standard absolute pressure,  760 mm Hg (29.92 in. Hg) .

                   Ideal  gas constant, 0.06236 [ (mm Hg) (m3) ] / [ (°K)  (g-mole) ] {21.85  [(-
                   in.  Hg) (ftJ)]/H°R) (lb-mole)]}.

-------
                                                      Section No. 3 .19.6
                                                      Date September 3,  1992
                                                      Page 2
Tm     =  Absolute average DGM temperature, °K (°R).

T.     =  Absolute average stack gas temperature, °K (°R).

T,ld    =  Standard absolute temperature, 293 °K  (528R).

V,c     =  Total volume liquid collected in impingers and silica gel, mL.

Vm     =  Volume of gas sample as measured by dry-gas meter, dcm (dcf).

vm.tdi   =  Volume of gas sample measured by the dry-gas meter, corrected  to
          standard conditions, dscm (dscf).

Vwi.cdi   =  Volume of water  vapor in the gas sample, corrected to  standard
          conditions,  scm (scf).

vs     =  Stack-gas velocity, calculated by Method 2,  Equation 2-9,  using
          data obtained from Method 5,  m/s (ft/s).

Y      =  Dry-gas meter calibration factor.

AH     =  Average pressure  differential across the orifice meter, mm H20 (in.
          H20).

pw     =  Density of water, 0.9982 g/mL  (0.002201 Ib/mL).

6      =  Total sampling time, min.
o
o
6j      =  Sampling time interval,  from the beginning of a run until the first
          component change,  min.

6,      =  Sampling time interval, between two successive component changes,
          beginning with the interval between the first and  second changes,
          min.

6P      =  Sampling time interval, from the final (nth)  component change until
          the end of the sampling run, min.

13.6   =  Specific gravity of mercury.

60     =  S/min.

100    =  Conversion to %.
                                                                            O

-------
 6.2
 6.3
6.4
                                                               Section No.  3.19.6
                                                               Date September 3,  19S2
                                                               Page 3
Conversion Factors

From

scf
g/ft3
g/ft3
g/ftj
                              To

                              m3
                              gr/ft3
                              lb/ft3
                              g/m3
Multiply by

0.02832
15.43
2.205 x 10°
35.31
Average Dry-Gas Meter Temperature and Average Orifice Pressure Drop

See data sheet (Figure 4.1).

Dry-Gas Volume
         Correct the sample volume measured by the dry-gas meter to standard conditions
 (20 °C, 760 mm Hg or  68  °F, 29.92 in. Hg) by using Equation 6-1.
                                                ^  AH ,
                            V=VmY
                             V = K, Vu Y
                                                                     Equation  6-1
where:

         Kj  =  0.3858  °K/mm Hg for  metric  units.

            • =  17.64 °R/in Hg for English, units.

         Note: Equation  6-1 can be  used as written unless the leakage rate observed
during any of the mandatory leak checks (i.e.,  the posttest  leak check or leak-checks
conducted prior to component changes) exceeds La.  If Lp or L, exceeds La, Equation  6-1
must be modified as follows:

(a)  Case I.  No component changes made during  sampling run.  In this case,  replace Vj
in Equation 6-1 with the  expression:

                                 [V, -  (L. - La)  6]

-------
                                                               Section No.  3 .19 .6
                                                               Date September 3, 199
                                                               Page 4
o
 (b)   Case  II.   One or more component  changes  made during the sampling run. In this
 case, replace Vm in Equation 6-1 by the expression:
                 (V. - (L, - La)  81 -    (L, -La)  6, - (Lp - L.)  8p]
                                      1-2

and substitute only for those leakage rates  (L, or Lp)  that  exceed La.

6 . 5      Volume of Water Vapor



                            Vw(.td, = vic  ^V^  = K2  Vle            Equation  6-2
                                         l-Lu CBtd

where :

         K2  = 0.001333 rn'/mL for metric units.

             = 0.04707 ftVmL for English units":"

6.6      Moisture Content
                                B   =      V"'stdl                     Equation  6-3
                                 us   17     nTlT
                                       vm(std)
                                                                                   O
         Note: In saturated or water droplet-laden gas streams,  calculate  the moisture
content of the stack  gas  in two ways: from the impinger analysis (Equation 6-3)  and
from the assumption of  saturated conditions.  The  lower  for  B,,. shall be considered
correct.  The procedure for determining the moisture content based upon assumption of
saturated conditions is given in the Note of Section 1.2,  Method 4.  For  the purposes
of this method,  the average stack-gas temperature from Figure  4.2 may  be  used  to make
this determination, provided  that the accuracy of the  in-stack  temperature sensor is
± 1 °C  (2 °F).

6.7      Nomenclature from Method 2

         A       =  Cross-sectional area of stack,  m2 (ft2).

         BU5      =  Water  vapor in the gas stream (from Method  5 or Reference Method
                    4),  proportion by volume.

         Ct.       =  Pitot  tube coefficient, dimensionless.

         K,,       =  Pitot  tube constant  -  34.97  for the metric system and 85.49 for
                    the  English system.

         Mj       =  Molecular weight  of  stack  gas,  dry  basis  (see Section 3.1
                    g/g-mole  (Ib/lb-mole).

         Mf       =  Molecular weight of stack gas,  wet basis,  g/g-mole (Ib/lb-mole).

-------
                                                                   Section No. 3.19.6
                                                                   Date September 3, 1992
                                                                   Page 5
                     =  Ma  (1  -  BW9)  + 18.0 Bw,

             Pb.r     =  Barometric pressure at measurement site, mm Hg  (in. Hg) .

             Pg      =  stack static pressure, mm Hg (in. Hg) .

             P.      =  Absolute stack pressure,  mm Hg (in. Hg) ,
D
6.8
             P.td


             Q.d
TBld

vs

Ap

3,600

18.0
                 =  Standard absolute pressure, 760 mm Hg (29.92 in. Hg) .

                 =  Dry volumetric stack gas  flow rate corrected to standard condi
                    tions,  dsmVh  (dscf/h) .

                 =  Stack temperature, °C (°F) .

                 =  Absolute stack temperature, °K (°R).

                 =  273 4- t,  for metric.        -*"

                 =  460 -*• t.  for English.

                 =  Standard absolute temperature, 293 °K (528 °R) .

                 =  Average stack gas velocity, m/sec (ft/s) .

                 =  Velocity head of stack gas, mm H20 (in.  H20) .

                 =  Conversion factor, s/h.

                 =  Molecular weight of water, g/g-mole (Ib/lb-mole) .
             Average Stack Gas Velocity
                               V  *
                                   CP <
                                                 Ts (avg)
                                                                         Equation 6-4

-------
6.9
6.10
Average Stack Gas,  Dry Volumetric Flow Rate
                         Q = 3600  (l-Bus) vsA
Isokinetic Variation
6.10.1   Calculation from Raw Data-
                100 T
                    I =
                                    V2c + (Vm -
                                              /n
                                     60 fc) vs
                                                            Section No. 3.19.6
                                                            Date September 3,  1952
                                                            Page 6
                                                                        o
                                                         Equation 6-5
                                                         Equation 6-6
where:
6.10.2
K3   =  0.003454 [(mm Hg) (m3)]/[(mL) (°K)] for metric units.
                                    -*"*
    =  0.002669 [(in.  Hg) (ft3)]/[(mL)(°R)], for English units.

Calculation from  Intermediate Values-


                 J  =
                              T  , v
                              •'•std vs
                              \n Pe 60  (1 - Bus)
                                                                  Equation 6
                                                                     -O
                      = K,
                                            v
                                         's ^m(std)
                                                                  Equation 6-E
where:
6.11
K4   =  4.320 for metric units.

    =  0.09450 for English units.

Acceptable Results
         If 90% 
-------
                                                               Section No.  3.19 .6
                                                               Date September  3,  1992
                                                               Page 7
6.12
Method...1.Q 1A Calculations
6.12.1   Determining Compliance-Each performance test consists of three repetitions of
the  applicable test  method.    For the  purpose of  determining compliance  with an
applicable  national  emission  standard,  use  the  average  of  the  results  of  all
repetitions.

6.12.2   Total Hg-For each source sample, correct the average maximum absorbance of the
two consecutive samples whose peak heights agreed within 3% of their average  for the
contribution of the blank.  Then calculate the total Hg content  in \ig in each  sample.
Correct  for any dilutions made  to bring the  sample  into the working  range of the
spectrophotometer.                 -•'-
                        m
                                   [C
                          (HCl)Hg
                                     (HCl}Hg
                                   DF]
where:
         m
          (HCUH9
          •(HCl blklHg
         DF
         DFh
                           [C
                             (HCl blklHg
                             DFblk]
                                  S
                                                       10
                                                         -3
                                                            Equation  6-9
                                   blk
             Total blank corrected Jig of  Hg  in HCl  rinse and HCl digestate
             of filter sample.

             Total ng of Hg analyzed in  the aliquot from the 500-mL Analysis
             Sample No. HCl A.2.                 :

             Total ng of Hg analyzed in aliquot of.the 500-mL Analysis Sample
             No HCl A.2 blank.

             Dilution  factor  for the HCl digested  Hg-containing solution,
             Analysis Sample No. HCl A.2.  This dilution factor (DF) applies
             only to  the intermediate dilution  steps  because  the original
             sample volume  (Vf)HC1 of HCl  A.2 has been factored  out in the
             equation, along with the sample aliquot,  (S) .  In Equation 6.9,
             the sample aliquot, S,  is introduced directly into the aeration
             cell for analysis according to the procedure  outlined in Section
             3.19.5.3.4.   A  dilution  factor  is  required  only  if  it   is
             necessary to bring the sample into the analytical instrument's
             calibration range.  If no dilution is necessary, then DF equals
             1.0.

             Dilution factor  for the HCl digested solution,  Analysis Sample
             No. HCl A.2 blank.  (Note:  Normal dilution factor calculations
             apply here.)

             Solution volume of original Analysis Sample  No. HCl A.2 andkHCl
             A.2 blank,  500 ml, for  samples  diluted as described  in Section
             5.2.2.4 of this  document.
         10'
          =  Conversion factor, ug/ng.

-------
                                                              Section No. 3.19. 6
                                                              Date September 3, 1BS2
                                                              Page 8

         S          =  Aliquot volume of  sample added to aeration cell,  mL.

         Sb)k        =  Aliquot volume of  blank added to aeration cell,  mL.

         Note: The maximum allowable blank subtraction for the HC1 is the lesser of the
two following values:  (1) the actual blank measured value (Analysis Sample No. HC1 A.2
blank); or  (2)  5% of  the Hg content in the combined HC1  rinse  and digested sample
(Analysis Sample No. HC1 A.2).
                                                                                      o
                     'imriHj
                                              V
                                               [([ltr].
where:
                                blk)Hg
                                             '
                                                      10
                                                         -3
                                      yblk
                                                                  Equation 6-1C
          (f UrlHg
          -If llrlHg
          Mfltr blklHg
                    =  Total  blank  corrected (Jg "of Hg  in KMn04 filtrate and HN03 di-
                       gestion of filter sample.
                    =  Total ng of Hg in aliquot of KMnO4  filtrate and HN03 digesticr.
                       of  filter analyzed  (aliquot of Analysis Sample A.I).
-o
                    = Total ng of Hg in aliquot of KMnO< blank and HNO, digestion cf
                      blank  filter analyzed  (aliquot  of Analysis  Sample No.  A.I
                      blank).
         Vt((Url       =  Solution  volume  of  original  sample,  normally  1000  mL  fcr
                       samples diluted as described in  Section 7.3.2 of Method  101A.

         V,lblkl        =  Solution volume of blank sample,  1000 mL for samples diluted as
                       described in Section 7.3.2  of  Method  101A.

Note: The maximum  allowable  blank subtraction  for the  HC1 is the lesser of  the  two
following values: (1) the actual blank measured  value  (Analysis Sample No.  A.I  blank;;
or (2) 5% of the Hg content in the filtrate (Analysis Sample No. A.I).
                                                                                      O

-------
                                                               Section No.  3.19.6
                                                               Date September  3,  1992
                                                               Page 9
                                                                    Equation  6-11
where:

         mHg       =  Total  blank corrected Hg content  in each  sample, fig.

         m(HciiH3    ~  Total  blank corrected \ig of Hg in HC1 rinse and HC1 digestate of
                     filter sample.

         mmtriHs   =  Total  blank corrected  Hg of  Hg in KMnO4  filtrate  and HNO3 di-
                     gestion of  filter sample.

6.12.3   Mercury Emission Rate-Calculate the Hg emission rate R in g/day for continuous
operations using Equation 101A-6 in Method 101A.   For cyclic operations, use only the
time per day each stack is in operation.  The total Hg emission rate from a source will
be the summation of results from all stacks.
where:
         A.

         86,400

         ID'6
          wist.


         T.


         PS

         K


         K
                          R = K
                                           (86,4^0 x 10'6)
                                               Equation 6-12
Total blank corrected Hg content in each sample, ug.

Average stack gas velocity, m/s  (fps).

Stack cross-sectional area, m2 (ft2).

Conversion factor, s/day.

Conversion factor, g/Jig.

Dry-gas  sample  volume  at  standard conditions,  corrected  for
leakage (if any), m3 (ft3).

Volume of water vapor at standard conditions, m3 (ft3) .

Absolute stack-gas temperature,  °K  (°R).

Absolute stack-gas pressure, mm  Hg  (in. Hg).

0.3858 °K/mm Hg  for metric units.

17.64 °R/in. Hg  for English units.

-------
                                                               Section  No.  3.19 .6
                                                               Date September 3,  1952
                                                               Page 10
6.13
Determining Compliance
                                          o
         Each performance test  consists  of  three repetitions of the applicable test
method.  For the purpose of determining compliance with an applicable national emission
standard, use the average of the results of all repetitions.
6.14
Hq Calculation for Alternate Analytical Systems
         For alternate analytical systems,  in which Hg is measured as a concentration
 (mg  Hg/L of sample)  the  Hg in mg  (m^)  in  the  original solution  is  calculated as
follows:
where:
CH

DF




V,
              = CHg x  (DF) x  (Vf)
                                                              Equation 6-12
              = Measured concentration of Hg in mg Hg/L of digested sample.

              = Dilution factor for the Hg-containing solution used to ensure measured
                sample  values were, within  the-c~def ined  portion of the  calibration
                curve.                            i
              = Solution volume of sample prepared in L.
                                                                                  O
                  TABLE 6.1   ACTIVITY MATRIX FOR CALCULATION CHECKS
Apparatus
       |Acceptance
       |limits
       I	
|Frequency and method
|of  measurement
                                                  |Action if
                                                   requirements
                                                   are  not met
Analysis
data form
       |All data and
       |calculations are
       I shown
(Visually check
I
                                        I
                                                   Complete the
                                                   missing data
Calculations
(Difference
|between  check and
(original
|calculations
|should not  exceed
(round-off error
                               (Repeat all
                               (calculations
                               (starting with raw
                               |data for hand
                               |calculations; check
                               |all raw data input
                               |for computer
                               (calculations; hand
                               (calculate one sample
                               (per test
                            Indicate  errors
                            on  calculation
                            form
                                                                                   O

-------
                                                                Section No.  3.19.7
                                                                Date September 3,  1992
                                                                Page 1


  7.0      MAINTENANCE

           The normal use of  emission testing equipment subjects it  to corrosive gases,
  extremes in temperature, vibration, and shock.  Keeping the equipment in good operating
  order requires  knowledge  of  the equipment  and a  program  of  routine maintenance
  performed quarterly or  after 1000 ft3  of operation, whichever is greater.  In  addition
  to  the  quarterly  maintenance,   cleaning  pumps  and metering  systems  annually  is
  recommended. Maintenance procedures for the various components are summarized in Table
  7.1 at the end of this  section.   The  following procedures are not required,  but  they
  are recommended to increase the  reliability of the equipment.

  7.1      Sampling Equipment

  7.1.1    Pump-Several types of pumps  may be used to perform Method 101A;  the  two  most
  common are the fiber vane pump with in-line oiler and the diaphragm pump.  The fiber
  vane pump  requires a periodic check of the  oiler jar.   Its contents should be  translu-
  cent;  the oil should be changed if not translucent.  Use  the  oil specified  by  the
  manufacturer.   If none  is specified,  use SAE-10 nondetergent oil.  Whenever  a fiber
  vane pump  starts to run erratically, or during  the yearly disassembly,  the head should
  be  removed and the fiber vanes changed.
          The diaphragm  pump requires  little maintenance.   If the diaphragm  pump leaks
  or  runs  erratically, it  is normally  due to a  bad diaphragm or malfunctions  in  the
{waives;  these  parts are easily  replaced and  should  be  cleaned annually by  complete
  disassembly of  the train.

  7.1.2    Dry-Gas  Meters—The  dry-gas  meter  should   be  checked for excess  oil   and
  component  corrosion by  removing the  top plate every 3 months.   The meter should be
  disassembled, and all components should be  cleaned and checked more often if the dials
  show erratic rotation or if the  meter will not calibrate properly.

  7.1.3    Inclined Manometer-The  fluid  should be changed  when it  is  discolored  or
  contains  visible  matter and  when it  is disassembled  yearly.   No  other  routine
  maintenance is  required because  the inclined manometer is evaluated during  the  leak
  checks of  both  the pitot tube and the entire meter box.

  7.1.4    Sampling Train-All  remaining sample  train components  should  be  visually
  checked  every  3 months,  and  they should  be  completely  disassembled and  cleaned or
  replaced yearly.  Many of the items, such as quick disconnects, should be replaced  only
  when damaged.

  7.2      Analytical  Instruments

  7.2.1    Spectrophoto/neter-Consult  the manufacturer's operation manual  for  specific
  maintenance activities.

  7.2.2    Peristaltic Pump TuJbing-Inspect pump  tubing daily.  The tubing should not  have
  flat spots  where it has contacted the pump rollers and should feel flexible.   Replace
  ubing if  this  is  not the case.                                                   ^ ^

  7.2.3    Desiccant-If a moisture trap is used instead of a heated  optical cell,  the
  desiccant  should be replaced daily.  Both tube ends should be filled with glass wool;
  the dessicant roust  not  be packed too  tightly.

-------
                                                               Section No.  3.19.7
                                                               Date September 3, 1992
                                                               Page 2
7.2.4    Optical Cell—The windows of the optical cell should be inspected daily for an;
dust,  dirt,  or grease  that will  degrade  light  throughput and  overall  analytical
performance.  Wash gently with  detergent and rinse well.  Dry by blotting with a towel
and wipe, if necessary,  with lens paper only.

7.2.5    Spectre-photometer Windows—The windows of the spectrophotometer must  also be
inspected (at least weekly) and cleaned as  described in section above.

7.2.6    Tygon Connecting Tubing-Connection tubing must be inspected on a daily basis
(or more frequently) for condensation or dirt.  Replace if
necessary.  The existence of moisture after the dessicant trap (if used)
indicates that the dessicant needs replacing.  Refer to Section 7.2.3.
o
                                                                                    o
                                                                                    o

-------
                                                                 Section No. 3.19.7
                                                                 Date September 3,  1992
                                                                 Page 3
                  TABLE 7.1  ACTIVITY MATRIX FOR EQUIPMENT MAINTENANCE CHECKS

-------
                                                              Section No. 3.19.7
                                                              Date September 3, 1992
                                                              Page 4
o
TABLE 7.1  Checks (Continued)
Apparatus
Analytical
Instruments
Spectro-
photometer
Peristaltic
pump tubing
Desiccant
Optical
cell
Spectro-
photometer
windows
Tygon
connecting
tubing
Acceptance
limits
1
See owner' s
manual
'
Flexible; no
flat spots
Fresh or dry
used silica gel;
no moisture
Clean of dust,
dirt, grease,
etc.
Same as above
No condensation
or dirt
Frequency and method
of measurement
. J .•;:••'
See owner's manual ,
manual
Visually inspect
tubing daily
Inspect daily
Inspect,-daily
:
Inspect weekly
Inspect daily
Action if
requirements
are not met
See owners
Replace
Replace
Clean gently
with detergent;
rinse; blot with
towel
Same as above
Replace
                                                                                     O

-------
                                                               Section No.  3.19.8
                                                               Date September 3,  1992
                                                               Page 1


 8.0      AUDITING PROCEDURES

         An  audit is  an  independent assessment of  data quality.   Independence is
 achieved when the persons performing the audit apply standards and  equipment different
 from  the standards and equipment  of the  regular field team.   Routine QA checks by a
 field team are  necessary to generate quality  data,  but they  are not part of the
 auditing procedure. Table 8.1 at the end of this section summarizes the QA functions
 for auditing.
         One performance audit is recommended when testing for compliance with National
 Emission Standards for Hazardous Air Pollutants  (NESHAPs), with New Source Performance
 Standards  (NSPS), and  as  required by other government agencies.  A performance audit
 is recommended when testing for other purposes; and two other performance audits are
 recommended.  The three performance audits are:
         1.    An audit of the analysis of Method 101A is recommended for NESHAPs.  The
               use of an NIST-traceable control sample is  recommended for NSPS testing
               and for  other  purposes.
         2.    An audit of the sampling is suggested by Method 101A and is recommended
               by the QA Handbook.
         3.    An audit of the data  processing  i,« also recommended.
         It  is  suggested that & systems audit  be  conducted as specified  by the QA
 coordinator in addition to these performance audits.  The two performance audits and
 the systems audit are  described in detail in Subsections 8.1 and 8.2, respectively.

 8.1      Performance Audits

         Performance audits are conducted to evaluate quantitatively the quality of
 data  produced  by the  sampling,  analysis,  or  the  total measurement  system  (sample
 collection, sample recovery, sample analysis, and data processing).

 8.1.1    Performance Audit of Method 101A Analysis—A performance audit for Method 101A
 analysis is recommended  for NESHAPs and  NSPS testing using  a control sample that is
NIST-traceable.   Although the control sample  values are known to the analyst,  the
 successful analysis of a  control sample,  as described in Subsection 5.3.3,  makes the
 results traceable to an NIST standard.

 8.1.2    Performance Audit of the Field Test—The dry-gas meter calibration should be
 checked by  one of the two  techniques  shown below (meter orifice check or critical
orifice check).

         Meter Orifice Check—Using the data  obtained  during the calibration procedure
described in Section 5.3, determine the AH,  for the metering  system orifice.   The AH,
 is the orifice pressure differential in units of in.  H20 that correlates to  0.75 cfm
of air at 528 °R  and 29.92 in. Hg.  The AHg  is calculated as  follows:


                                      =   "	§__                  Equation  8-1
         AH   =  Average pressure differential across the orifice meter, in. H20

-------
                                                              Section No. 3.19.8
                                                              Date September 3,  1992
                                                              Page 2
         Tm   =  Absolute average DGM temperature, °R.

         Pt»r  =  Barometric pressure, in. Hg.

         6    =  Total sampling time, min.

         Y    =  DGM calibration factor, dimensionless.

         VK   =  Volume of gas sample as measured by DGM,  dcf.

         Before beginning the  field  test (a set of three  runs  usually constitutes a
field test), operate the metering system (i.e., pump, volume meter,  and orifice) at the
AH, pressure differential for 10 min.  Record the volume collected,  the DGM tempera-
ture, and the barometric  pressure.   Calculate  a DGM calibration check value, Yc, as
follows:
                                                                                     o
                                           TTJT19 Tm
                                              • bar
                                                                    Equation  8-2
where:

         Yc       =  DGM calibration check value,  dimensionless.

         10       =  Run time,  min.

         0.0319   =  (0.0567 in Hg/°R)(0.75 cfm)2.

         Compare  the Yc  value with  the  dry-gas  meter  calibration  factor,  Y,  tc
determine that:  0.97Y 
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Vcrlatd)   =  K'


Y       =  V
                                                               Section No.  3.19 .8
                                                               Date September 3,  1992
                                                               Page 3

                                                                        Equation 8-4

                                                                        Equation 8-5
 where:
         vcristdi   =  Volume of gas sample passed through the critical orifice,-—correct-v
                    ed to standard conditions,*dscm (dscf).

         K'      =  0.3858 °K/mm Hg for metric units      ...              •    •

                 =  17.64 °R/in Hg for English units.

         7.    Average the DGM  calibration  values  for each of the flow rates.  The
               calibration factor, Y,  at each of the flow rates should not differ by
               more than ± 2% from the average.                       .        ...

8.1.3    Performance  Audit  of Data Processings-Calculation errors are prevalent when
processing data.   Data processing errors can be determined by auditing the  recorded
data on the  field and laboratory forms.  The  original and audit  (check) calculations
should agree within  round-off  error;  if not, all, of the remaining  data should be
checked.  Data processing also may be audited by requiring that the testing laboratory
 rovide an  example calculation  for one  sample,run.  This  example calculation will
 nclude all the calculations used to determine the emissions based on the raw field and
laboratory data.                                                      . :
8.2
System Audit
         A system audit is an on-site, qualitative inspection and review of  the  total
measurement  system.   Initially, a system  audit  is recommended for each enforcement
source test, defined here as a  series of three runs at a source.
         The auditor should have extensive background experience with  source sampling
or source test observation, specifically with Method 101A or Method 5.   The.  auditor-'•&•
functions are summarized below:
         1.   Observe  procedures  and techniques  of the  field  team  during sample
              collection and sample recovery.
         2.   Check/verify records of apparatus calibration checks and QC used in the
              laboratory analysis.    .    .   ...
         While  on-site,  the   auditor  observes   the  source   test  team's  overall
performance, including the  following  specific operations:
         1.   Setting up the sampling system and checking  the  sample train  and  pitot
              tube  for  leaks.
         2.   Collecting the isokinetic  sampling.
         3.   Conducting the final leak  checks.
         4.   Sample documentation procedures, sample recovery,  and preparatipn of the
              samples for shipment.
Figure 4.3  in Section  3.19.4  is  a  suggested field observation  checklist   for  101A
sampling and sample  recovery, and Figure 5.9 in Section 3.19.5 is a suggested  checklist
 or 101A sample analysis.                                                         "• -

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                                                                Section No. 3.19.8
                                                                Date September 3, i992
                                                                Page 4
                  TABLE 8.1  ACTIVITY MATRIX FOR AUDITING PROCEDURES
                                                                       o
Apparatus
I
|Acceptance
|limits
I
(Frequency and method
|of measurement
I Action if
(requirements
|are not met
Performance
audit of
analytical
phase
(Measured
(relative error of
(audit samples
(less than 15%
| (or other stated
(value)  for both
|samples
                1
I Frequency;  Once
|during every
|enforcement source
(test"             '"
(Method;  Measure
|audit  samples and
|compare results to
|true values
|Review
(operating
|technique and
|repeat audit
Volumetric
sampling
(Measured pretest
(volume within
|± 10% of the
(audit volume
I
I Frequency;  Once
|during every
|enforcement source
(test'
(Method; -^Tleasure
|reference volume and
|compare with true
|volume
I
|Review
(operating
|techniques
                                                                                       O
Data
processing
errors
(Original and
|checked
|calculations
(agree within
(round-off error
I
(Frequency;  Once
|during every
(enforcement test"
(Method; Independent
|calculations
|starting with
|recorded data
|Check and
|correct 'all data
|for the audit
(period
|represented
(by the
|sampled data
I         ______
Systems
audit-
observance
of
technique
(Operational
|technique as
(described in
(this section of
(the Handbook
I
I Frequency;  Once
|during every
|enforcement source
(source test" until
|experience gained,
|then every third
(test
(Method; Observation
(of techniques
(assisted by audit
(checklist (Fig. 4.2)
(Explain to team
(their deviations
(from recommended
|techniques and
(note on Fig.  4.2
I
•As defined here, a source test, for enforcement comprises a series of three runs at one source.  Source test
for purposes other than enforcement may be audited at  the frequency determined by the applicabl-s group.
                                                                                       O

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                                                              Section No.  3.19.9
                                                              Date September 3, 1992
                                                              Page 1
         RECOMMENDED STANDARDS FOR ESTABLISHING TRACEABILITY
         To  achieve  data  of  desired  quality,  two  essential  considerations  are
necessary: (1) the measurement process must be in a state of statistical control at the
time of the measurement; and (2)  the systematic  errors, when combined with the random
variation (errors or measurement), must result in an acceptable uncertainty.  Evidence
of  quality  data  results  from performing  QC checks and  independent audits  of the
measurement process,  documenting these data, and using materials,  instruments, and
measurement procedures that can be traced to an appropriate standard of reference.
         Data must  be  routinely  obtained  by repeatedly measuring standard reference
samples (primary, secondary, and/or working standards) and by establishing a condition
of process control.   The working  calibration standards  must be traceable to standards
of  higher accuracy  by using a control  sample or by purchasing  working calibration
standards that are NIST-traceable.
         Performance  audit samples  are  not required  for determining  compliance;
however, an NIST control  sample  is  recommended  (as  discussed  in  Section 3.19.8) .   A
control sample is also recommended as an independent check on the measurement process
when  the  method  is performed for  other  purposes.   This procedure makes  all the
compliance determination samples traceable to an NIST standard.
/I1-
                                                li!

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o
o
o

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                                                            Section No. 3.19.10
                                                            Date September  21,  1992
                                                            Page 1


 10.0      REFERENCE METHODS:  METHOD 101A-DETERMINATION OF PARTICIPATE  AND  GASEOUS
           MERCURY EMISSIONS FROM STATIONARY SOURCES

           This  method is similar to Method 101,  except  acidic potassium permanganate
 solution is used instead of acidic iodine monochloride  for sample collection.

 1.0       APPLICABILITY AND PRINCIPLE

 1 -1       Applicability

           This method applies to determining particulate and gaseous Hg emissions from
 sewage sludge incinerators and other sources,  as specified in the regulations.

 1-2       Principle

           Particulate and  gaseous  Hg emissions are withdrawn isokinetically from the
 source and  collected  in  acidic potassium  permanganate  (KMnO<)  solution.    The Hg
 collected  (in mercuric form) is reduced to elemental Hg,  which is then aerated from the
 solution into an optical cell  and  measured by  afc"3mic absorption spectrophotometry.

 2.0       RANGE  AND SENSITIVITY

 2.1       Range

           After  initial dilution, the range of  this method is 20 to 800 ng  Hg/mL.   The
 upper  limit  can  be  extended by further dilution  of the  sample.

 2.2       Sensitivity

          The sensitivity  of  the  method  depends  on  the recorder/spectrophotometer
 combination  selected.

 3.0        INTERFERING AGENTS

 3.1       Sampling

          Excessive oxidizable matter in the stack-gas prematurely depletes the KMnO<
 solution and, thereby,  prevents further  collection of Hg.                         •
This section represents Method  101A and  referenced procedures  from Method 101.   Text
from Method 101 is shown in bold  italics.

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                                                            Section No. 3.19.10
                                                            Date September 21, 1992
                                                            Page 2
3.2       Analysis
o
          Condensation of  water vapor  on  the optical cell  windows  causes positive
interference.

4.0       PRECISION

          Based on eight  paired-train tests,  the  within-laboratory standard deviation
was estimated to be 4.8 jag/mL in the  concentration range of 50 to 130 Jlg/m1.

5.0       APPARATUS

5.1       Sampling Train and Sample__Recovery

          Same as in Method  101, Sections  5.1 and 5.2,  respectively,  except for the
following variations:

5.1.1     Probe Nozzle,  Pitot  Tube,  Differential Pressure Gauge, Metering System,
Barometer, and Gas Density Determination Equipment—Same as in Method 5, Sections 2.1.1,
2.1.3, 2.1.4, 2.1.8, 2.1.9,  and 2.1.10, respectively.
5.1.1     Probe Liner—Borosilicato or quartz glass tubing.   Tenters may ueo a hooting
ay-atom capable of maintaining a gas tojuperaturo of 120 ± 14 °C (248 ± 25 °F) at the
probe exit  during  campling to prevent orator  condemnation.   (Notes  Do not ueo metal
probo liners.)
          If a  filter is used  ahead of  the  impingers,  testers must use  the prob
heating system to minimize the condensation of gaseous Hg.   If a filter is used ahead
of  the  impingers,   testers  must  use  the probe heating  system  to minimize  the
condensation of gaseous Hg.
 O
5.1.2     Filter Holder (Optional)—The holder should be composed of borosilicate glass
with  a rigid  stainless-steel  wire-screen  filter  support  (do  not  use  glass  frit
supports) and a silicone rubber or Teflon gasket,  designed to provide a positive  seal
against leakage from outside or around the filter.  The filter holder must be equipped
with a  filter heating  system capable of maintaining a temperature around the filter
holder of 120 ±  15 °C (248  ±  25  °F) during  sampling to minimize  both water and gaseous
Hg condensation.   Testers  may use a filter  in cases where the stream contains large
quantities of particulate matter.

5.1.3     Impingers-Four  Groonburg-Sndtb  impingers  are  required.   They  should  be
connected in series with leak-free  ground glass  fittings or any similar leak-free,
noncontominating fittings.  For the firat,  third, and fourth impingersf tenters may use
impingors that are modified by replacing the tip with a 13-nxn ID (0.5-in.) glass  tube
extending to 13 mm (0.5 in.)  from the bottom of the  flask.
                                                                                     O
                                                       /;

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                                                             Section No. 3.19.10
                                                             Date  September  21,  19&2
                                                             Page  3

 5.2       Sample Recovery                                            . • ...      ...  .

           The following items are needed for sample recovery:

 5.2.1     Glass  Sample Bottles-The bottles should be leakless, with Teflon-lined cape,
 1000 and 100 ml/.

 5.2.2     Graduated Cylinder—A 250-mL graduated  cylinder  is  required.

 5.2.3     Funnel and .Rubber Policeman—These items aid in transferring silica gel to the
 container; they are not necessary if the silica  gel 10 weighed in the field.

 5.2.4     Funnel-The funnel  should be glass/  it  aids in sample  recovery.

 5.2       Analysis

           Same as in Method 101, Sections 5.3 and  5.4, respectively, except  as follows:

 5.2.1     Volumetric Pipets-Pipets must  be  Class A, 1,  2, 3, 4, 5, 10, and  20 mL.

 5.2.2     Graduated Cylinder—A 25-mL graduated cylinder is required.

  .2.3     Steam  Bath-Same  as  Method  101.

 5.3        Sample  Preparation  and  Analysis

           The following  equipment  is needed for  sample  preparation and analysis:

 5.3.1     Atomic Absorption Spectrophotometer—Any atomic absorption unit is  suitable,
 provided  it  has  an  open  sample presentation area in which to mount  the optical  cell.
 Testers should follow the instrument  settings recommended by the manufacturer.  Instru-
 ments designed specifically for measuring Hg using the cold-vapor technique are commer-
 cially available  and may be  substituted  for the  atomic  absorption Spectrophotometer.

 5.3.2      Optical Cell—The optical cell should be cylindrical, with quartz end wlndovs
 and  the dimensions  shown in  Figure 101A-2.  Wind the cell with approximately 2 m of
 24-gauge nichrome heating wire and wrap with fiberglass  insulation  tape, or equivalent;
 do not let the wires touch one another. As an alternative  to the heating wire,  tester-
may use a heat lamp  mounted above the cell or a moisture  trap installed upstream of ths
 cell.

 5.3.3     Aeration  Cell-Tie coll must be constructed according to the specifications
 in Figure  101A-3.  Do not use a glass frit as a substitute for the blown glass bubbler
 tip  shown in Figure  101A-3.   Aeration  cells, available  with  commercial ccld-vapcr
 instrumentation, may  be  used  as an alternate  apparatus.

5.3.41     Recorder—The recorder must be  matched to output  of  the  Spectrophotometer
 escribed  in Section  5.3.1.
                                                                                  V
5.5.5     Variable Transformer-The transformer is necessary for  varying the voltage en
the optical cell from 0  to 40 volts.

5.3.6     Hood-A hood is required for venting the optical cell  exhaust.

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                                                            Section No.  3.19.10
                                                            Date September 21, 1992
                                                            Page 4
5.3.7     Flow Metering Valve-Same as Method 101.
o
5.3.8     Flow Meter—A  rotometor,  or equivalent,  la  required  that  IB  capable of
measuring a gao flow of 1.5 L/mln.

5.3.9     Aeration Gas Cylinder—The cylinder must contain nitrogen or dry, Hg-free air
and must be equipped with a single-stage regulator.  As an alternative,  aeration may
be provided by a peristaltic metering pump.   If a  commercial cold-vapor instrument is
used, follow the manufacturer's recommendations.                .

5.3.10    Tubing-Tho tubing ia require  for making connections.   Deo  glass tubing
(ungreaaed ba.ll* and socket-connections arc recommended) for all connections between
the  solution  cell and  the  optical  cell;  do not  UBO  Tygon tubing,  other  types of
flexible tubing, or metal tubing  as eubntltuten.   Teeters may use Teflon, stool, or
copper tubing between the nitrogen tank and the flow meter valve  (Section 5.3.7), and
Tygon, gum, or rubber tubing between  the flow meter valve and the aeration cell.

5.3.11    Flow Rate Calibration Equipment—This  equipment consists of a  bubble flow
meter or a wet-test meter for measuring a gas flow rate of 1.5 ± 0.1  L/mln.

5.3.12    Volumetric Flasks—Those  flasks must be Class A, with ponnyhoad standard taper
stoppers; the required sizes are  100, 250, 500,  and 1000 mL.
5.3.13    Volumetric Pipets-Thoso plpots must bo Class A; the required sizes are 1, 2,
3, 4, 5, 10, and 20 mL.
5.3.14    Graduated Cylinder—A 25-mL cylinder is required.

5.3.15    Magnetic Stirrer—A general-purpose laboratory-type stirring bar is required.

5.3.16    Magnetic Stirring Bar—A Teflon-coated stirring bar is required.

5.3.17    Balance-A balance capable of weighing to ± 0.5 g is required.

5.3.18    Steam Bath
O
                                                                                    o

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                                                            Section No. 3.19.10
                                                            Date September 21, 1992
                                                            Page 5

 5.4       Alternative  Analytical Apparatus

           Alternative  systems  are allowable  as  long  as  they meet  the following
 criteria:

 5.4.1     The  system must generate  a  linear calibration  curve and two  consecutive
 samples of  the  same aliquot size and  concentration must agree within  3% of their
 average.

 5.4.2     The  system must allow for recovery of a minimum of 95% of the spike  when an
 aliquot of a source sample is spiked with a known concentration of Hg  (II) compound.

 5.4.3     The  reducing agent should be added after the aeration cell is closed.

 5.4.4     The  aeration bottle bubbler should not  contain a frit.

 5.4.5     Any  Tygon  tubing  used  should be  as  short  as possible  and  should be
 conditioned prior to  use until  blanks  and standards yield linear and reproducible
 results.

 5.4.6     If manual stirring is performed before aeration, the aeration cell should be
 closed during  the process.

 5.4.7     A  drying  tube should not  be  used unless  it  is  conditioned following the
 procedure for  the Tygon  tubing, above.

 6.0        REAGENTS

           Use ACS reagent-grade chemicals or equivalent, unless otherwise specified.

 6 .1        Sampling and Recovery

           The following reagents are used in sampling and recovery:

 6.1.1      WaCer-Deionized distilled, meeting ASTM specifications for Type I  Reagent
 Water—ASTM Test  Method D'1193-77.   If  high  concentrations of organic matter  are not
 expected  to  be present, users  may eliminate the KMnO4  test  for oxidizable  organic
 matter.   Use this water  in all dilutions and solution preparations.

 6.1.2      Nitric Acid  (HNO,), 50%  (v/v)-Hix equal volumes of  concentrated HN03 and
 water, being careful to add  the acid to the water slowly.

 6.1.3      Silica Gel-Indicating type, 6- to 16-mesh.  If previously used,  dry at 175
 °C  (350 °F)  for 2 h.   Testers may use new silica  gel as  received.

 6.1.4      Filter (Optional;-Glass fiber  filter, without  organic  binder, exhibiting at
 least 99.95% efficiency on 0.3-nm dioctyl phthalate smoke particles.   Testers  may use
 the  filter in  cases where the  gas stream contains  large  quantities of  particulate
matter, but they should analyze blank filters for Hg content.                   <,

 6.1.5     Sulfuric Acid (H:SO.),  10%  (v/v)-Add and mix 100 mL of concentrated  H;SO. to
 900 mL of  water.

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                                                            Section No. 3.19.10
                                                            Date September 21, 1992
                                                            Page 6
6.1.6     Absorbing Solution,  4%  KMnO,  (WvJ-Prepare  fresh daily.   Dissolve
KMnO< in sufficient  10% H;SO,  to  make 1 L.   Prepare  and store  in  glass bottles to
prevent degradation.                                                               :

6.1.7     Hydrochloric Acid—Trace metals grade HCl is recommended.  If other grades are
used, the Hg level must be  less than  3  ng/mL Hg.

6.1.8     Hydrochloric Acid, 8 ^-Dilute 67 mL of concentrated HCl to  100 mL with water
(slowly add the HCl to  the  water).

6.2       Analysis

          The reagents needed  for analysis are listed below:

6.2.1     Tin (II) Solution-Prepare fresh daily and keep sealed when not being used.
Completely dissolve 20 g of tin (II)  chloride [or 25 g of tin (II) sulfate] crystals
(Baker Analyzed reagent grade  or any  other brand that will give a clear solution) in
25 mL of concentrated HCl.   Dilute to 250 mL with water.  Do not substitute HNO3, H;SO,.,
or other strong acids for the  HCl. .            .

6.2.2     Sodium Chloride-Hydroxylamine Solution—Dissolve 12  g of sodium chloride and
12 g of hydroxylamine sulfate  (or 12  g of hydroxylamine hydrochloride)  in water and
dilute to 100 mL.

6.2.3     Hydrochloric Acid, 8 J\HDilute 67 mL of concentrated HCl to  100 mL with
(slowly add the HCl to the  water).

6.2.4     Nitric Acid,  15%  (v/v)-Slouly add  15  mL of  concentrated HN03  to 100 mL of
water.

6.2.5     Mercury  StocJc Solution,  1  mg Hg/mL-Prepare  and   store  all   Hg standard
solutions in borosilicate glass containers.  Completely dissolve 0.1354 g  of  Hg  (II)
chloride in 75 mL of  water.  Add  10 mL of  concentrated  HNO3 and adjust the volume to
exactly 100 mL with water.   Mix thoroughly.   This solution is stable for at  least 1
month.

6.2.6     Intermediate Hg Standard Solution, 10 jig/mL-Prepare fresh weekly.  Pipet 5.0
mL of the Hg stock solution  (Section 6.2.5) into a 500-mL volumetric  flask, and add 20
mL of 15% HNOj  solution.  Adjust the volume to exactly 500 mL with water.   Thoroughly
mix the solution.

6.2.7     Working Hg  Standard  Solution, 200 ng Hg/mL-Prepare  fresh daily.   Pipet 5.0
mL from the Intermediate Hg  Standard Solution  (Section 6.2.6)  into a  250-mL volumetric
flask.  Add 5 mL of 4% KMnO,  absorbing  solution and 5 mL of 15% HNO,.  Adjust che volume
to exactly 250 mL with  water.   Mix thoroughly.

6.2.8     Potassium Permanganate, 5%  fw/vJ-Dissolve 5 g of KMnO< in water  and dilute
to 100 mL.
6.2.9     Filter—Use a Whatman 40, or equivalent.

7 .0       PROCEDURE
o

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                                                            Section No. 3.19.10
                                                            Date September 21, 1992
                                                            Page 7
 7.1.
Sampling
           The  sampling procedure is  the  same as in Method  101,  except for changes
 associated with using  KMnO4 instead of IC1 absorbing solution and  the possible use of
 a filter.   Because of the  complexity of this method,  teeters  should be trained and
 experienced with all procedures  to ensure reliable results.  Because  the amount  of Kg
 collected  generally is small,  the method must be applied carefully to prevent sample
 contamination  or loss.

 7.1.1      Pretest Preparation—Follow  the general procedure  given in Method 5, Section
 4.1.1,  but omit the directions on the filter.

 7.1.2      Preliminary  Determinations—The  preliminary determinations  are the same as
 those given in Method  101, Section 7.1.2, except for the absorbing solution depletion
 sign.   In  this  method, high-oxidizable organic matter content may make  it impossible
 to  sample  for  the desired minimum time.   This problem  is  indicated  by the complete
 bleaching  of the purple  color of the KMnO< solution.   In these  cases,  testers may
 divide  the sample run  into  two or more subruns to ensure that the absorbing solution
 will not be depleted.   In cases where excess water  condensation is encountered, collect
 two runs to make one sample.                    H~
7.1.2
Sampling Train Preparation
7.1.2.1   Sampling train preparation is the same as that  given in Method 101, Section
7.1.3,  except for  the  cleaning  of  the glassware  (probe,  filter holder,  if used,
impingers, and connectors) and for the  charging  of the first three  impingers.   In this
method, clean all the glass  components by  rinsing  with 50%  HN03/ tap water,  8 N HCl,
tap water, and finally deionized distilled water.  Then place 50 mL of 4% KMnO< in the
first impinger and 100 mL in each of the second and third impingers.

7.1.2.2   If a filter is used, place it with the  filter holder with a pair of tweezers.
Be sure to center the filter, and place the gasket in the proper position to prevent
the sample gas stream from by-passing the filter. Visually check the filter for damage
after assembly is completed.  Be sure to set the filter heating  system at the desired
operating temperature after  the  sampling train  has been  assembled.

7.1.2.1   Follow the  general procedure given in Method  5,  Section 4.1.2,  except  as
follows:  Select a nozzle size based on the range of velocity heads to ensure  that  it
is not necessary to change the nozzle size  to maintain isokinetic sampling rates below
28 L/min  (1.0 cfm).

7.1.2.2   Highly oxidizable organic content may make it  impossible to sample  for the
desired minimum  time.   This problem  is indicated by the  complete bleaching of the
purple  color  of the KMnO4 solution.   If  the purple  color is  expended  in  the last
(third) KMnOt  impinger,  the  sample run  is unacceptable and  another run  shall  be
conducted.  In these cases,  testers may divide the sample run into  two or more  subruns
to ensure  that the  absorbing solution will  not be  depleted  or  a  fourth impinger
containing 100 mL of KMnOt may be used.  In cases where  excess water condensation  is
encountered, collect two runs to make one sample  or  add extra empty impinger before the
first impinger containing KMnO4 solution.

7.1.3     All  the glass components should  been  cleaned  in  the  laboratory (a hood  is
recommended) by soaking with 50% HNO, for  1 h and then by rinsing with tap water, B N

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                                                            Section No. 3.19.10
                                                            Date September 21, 1952
                                                            Page 8   ......
                                               • •<-.•••:•'     •.  .. • •-.(-.   •   .     .-:••••.
HC1, tap water,  and finally deionizod distilled water.  After cleaning, openings shou
bo covered to prevent contamination.

7.1.3.1   Place 50 mL  of 4% KMnO< in the  first  impinger and 100 tnL  in  each of  the
second  and  third  impingers.   Take  care  to  prevent  the  absorbing  solution frc.-n
contacting any greased surfaces.  Place approximately 200 g of preweighed silica  gel
in the fourth impinger.  Testers may use more  silica gel, but they should be  careful
to ensure that it is not entrained and carried out from  the impinger during sampling.
Place the silica gel container in a clean place, for later use  in  the sample recovery.
Alternatively, determine and record the weight of. the silica gel  plus  impinger to  the
nearest 0.5  g.  (Note: Contact with KMnO4  should be avoided.)

7.1.3.2   If a filter is used,  place it  in the filter holder with a pair of tweezers.
Be sure to center  the filter, and place the gasket in the proper position to  prevent
the sample gas  stream  from  by-passing the filter.  Check the filter for tears after
assembly  is  completed.   Be sure  to  set  the  filter heating system  at  the  desired
operating temperature after  the sampling  train has been assembled.

7.1.3.3   Install tho selected nozzle using a  Viton A O-ring when Btack temperatures
are less  than  260  °C (500 °F).  UBO a  fiborgldss string gasket  if temperatures  are
higher.  Other connecting systems uaing either 316\stainloss-stool or Teflon ferrules
may bo used.  Mark  the probe with heat-resistant tape  or by some other method to denote
tho proper distance into the  stack or duct for each sampling point. Assemble the train
an shown in  Figure 101A-1,'using  (if necessary) a very  light coat of silicone gre&s~*<.
on all ground glass Joints.  Grease only  the outer portion to avoid contamination^   1
tho oiliconc grease.                                                              ^—^
          Note: An  empty impinger may be inserted between the.filter and firsc impinc--£r
containing KMnO< to remove excess moisture from the sample stream.

7.1.3.4   After tho sampling train has been assembled,  turn on and set the probe, if
applicable, at tho desired operating temperature.   Allow time  for the  temperatures to
stabilize.   Place crushed ice around tho  iopingors.

7.1.4     Leak Check Procedures-Follow the leak chock procedures outlined in Hethod 5,
Sections A.I.A.I, 4.1.4.2, and 4.1.4.3.

7.1.3     Sampling Train Operation—In addition to the procedure  given  in Method.3.01,
Section 7.1.5, maintain a temperature around tho filter  (if applicable) of-,120 * 14 °C
(248 ± 25 °F).

7.1.5     Mercury  Train  Operation-Follow  the  general procedure given in Method 5,
Section 4.1.5, maintain a temperature around the filter  (if applicable) of 120 * 14 .°C
(248 ± 25 °F) .   For each run, record tho data required on a data sheet, such as the  one
shown in Figure 101A-4.

7.1.6     Calculating  Percent  of Isokinetic  Sampling—Same  as in' Method 5,   Section
4.1.6.
1.2       Sample Recovery
;D
          Begin proper cleanup procedure as soon as the probe is removed from the s
at the end of the sampling period.  Allow the probe  to cool.  When  it  can  be  handled
safely, wipe off any external particulate matter  near the  nozzle  tip and place a  cap

-------
                                                            Section No. 3.19.10
                                                            Date September 21, 1951
                                                            Page 9

 over it.  Do not cap the probe tip tightly while the sampling train  is cooling because
 the  resultant vacuum would  draw  liquid  from the impingers.  Before moving the sample
 train to the cleanup site,  remove  the  probe from the train, wipe off the  silicons
 grease,  and  cap  the  open outlet  of  the  probe.  Be careful not to lose any condensate
 that might be present.   Wipe the  silicone grease  from  the impinger.   Use either
 ground-glass stoppers, plastic caps, or serum caps to close  these openings.   Transfer
 the  probe, impinger  assembly,  and  (if applicable) filter assembly  to an area that is
 clean, protected from the wind,  and free of Hg contamination.
          The ambient air in laboratories located in the immediate vicinity of  Hg-using
 facilities is  not normally free of Hg  contamination.  Inspect  the train before and
 during assembly  and  note any abnormal conditions.  Treat the sample as follows:

 7.2.1     Container Wo.  1 (Impinger, Probe, and Filter Holder) and,  if Applicable, No.
 1A  (HC1  Rinse)

 7.2.1.1   Using a graduated cylinder,  measure the liquid in  the first three impingers
 to within 1 mL.  Record  the  volume of liquid present  (see  Figure  5-3 of  Method 5 in 41
 CFR  Part 60).   This information is needed to calculate the moisture  content of the
 effluent gas.  (Use  only graduated  cylinder and glass storage bottles that have beer.
 precleaned as  described in  Section 7.1.2)   Pla"ce  the  contents of the  first three
 impingers into a  1000-mL glass sample bottle.  Note: If a filter is used, remove the
 filter from its  holder,   as  outlined under Container No. 3 below.

 7.2.1.2   Taking care that  dust on the outside of the probe or other exterior  surfaces
 does not get into the sample, quantitatively recover the Hg  (and any condensate) fron
 the probe nozzle, probe   fitting,  probe liner,  and front half of the filter holder  (if
 applicable) and  impingers as  follows:   Rinse these components with a total of 400 r.L-
 of fresh 4% KMnO^  solution,  carefully ensuring removal of all loose  particulate matter
 from the impingers.  Add all washings  to the 1000-mL glass sample bottle.  Remove ar.y
 residual  brown  deposits on  the glassware  following the  permanganate  rinse  with
 approximately 100  mL of water,  carefully assuring  removal  of all  loose particulate
matter from  the  impingers,   and  add this rinse to  Container No.   1.   If no visible
deposits remain  after  this water rinse,  do not rinse with 8  N HC1.    However, if
deposits do  remain on the  glassware after the water rinse,  wash   impinger walls ar.d
stems with the  same 25 mL of 8 N HC1  and  place the wash in  a separate container labeled
Container No.  1A.   Use   the  following procedure:  Place 200 mL of  water  in  a sample
container labeled Container No. 1A.  Use only a total of 25 mL of 8  N HCl  to rinse ell
 impingers.  Wash the impinger walls and stem with the HCl by turning and shaking the
 impinger so that the HCl contacts all inside surfaces.  While stirring, pour the KC1
wash  carefully  into Container No.  1A.   The  separate container is used for safety
reasons.

7.2.1.3   After all washings have been collected in  the sample container, tighten the
 lid to prevent  leakage during shipment to the laboratory.  Mark the height of the  fluid
 level to help determine  whether leakage  occurs during transport.  Label the container
to identify its contents clearly.

7.2.2     Container Wo.  2 (Silica GeJ^-Note  the  color of the indicating silica gel tc
determine whether  it has been completely spent and make a notation of  its ccnditifen..
Transfer the silica gel from its   impinger to  its  original container  and  seal  the
container. A funnel may be  used  to  pour the silica gel, and  a rubber policeman may be
used to remove the silica gel from  the  impinger.   It is  not necessary to remove  the
small amount of  particles that may  adhere  to the impinger wall  and are difficult t:

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                                                             Section No. 3.19.10
                            .              •                   Date September' '21,  1992
                                            .  .   .            Page 10           -

 remove.  Because the weight gain is to be used for moisture  calculations,  do  not  use
 any water or other liquids to transfer the silica  gel.   If a balance  is available in
 the field,  weigh the spent silica gel (or silica gel plus impinger)  to the  nearest  0.5
 g and record this weight.                                     .

 7.2.3     Container No.  3  (Filter)—If a  filter was used, carefully remove  it from  the
 filter holder, place it in a  100-mL glass sample  bottle,  and add  20 to 40 mL of 4%
 KMnO<.   If  it is necessary to fold the  filter, be  sure that  the particulate  cake is
 inside the  fold.  Carefully transfer to the 150-mL sample bottle any particulate matter
 and filter  fibers that adhere to the filter holder  gasket by using a  dry Nylon  bristle
 brush and a sharp-edged blade.   Seal the container.  Label the container  to identify
 its contents clearly.   Mark the height  of  the  fluid  level to help determine  whether
 leakage occurs during  transport.

 7.2.4     Container No.  4  (Filter Blank)—It a filter was used, treat  an unused filter
 from the same filter lot used for  sampling in the  same  manner as Container No. 3.

 7.2.5     Container No.  5  (Absorbing Solution Blank)—For a blank, place 650 mL of  4 %
 KMnO., absorbing  solution in a 1000-mL sample bottle.  Seal the container.
                                                .-r~
 7.2.6     Container No.  6 (HCl Rinse Blank)—For a blank, place 200  mL of  water in a
 1000-mL sample bottle.  While  stirring, add  25 mL of 8 N HCl.   Seal  the  container.
 Only one blank sample  per 3 runs is required.

 7 .3       Sample Preparation

           Check  the liquid level in each container to  see if liquid was  lost during
 transport.   If a noticeable amount  of leakage occurred,  either void  the sample or  use
 methods subject  to the  approval of  the Administrator to account for  the losses.  Then
 follow the procedures  below:

 7.3.1     Containers No.  3 and No.  4 (Filter  and Filter Blank)-I£ a  filter was used,
 place the contents, including the  filter,  of Containers No.  3 and No. 4  in separate
 250-mL beakers.   Heat  the  beakers on  a  steam bath until  most of  the   liquid  has
 evaporated.  Do not take to dryness.  Add 20 mL of concentrated HNO3  to the beakers,
 cover them with  a watch glass,  and  heat  on a hot plate at 70  °C for  2 h.   Remove  from
 the hot plate.  Filter the solution  from  the digestion of the  contents of Container No.
 3 through Whatman 40 filter paper and save  the  filtrate for addition to the Container
 No. 1 filtrate,  as  described below.  Discard the filter.  Filter the  solution  from the
 digestion of the contents  of  Container No.  4 through Whatman  40 filter paper and save
 the filtrate  for addition  to  the  Container No. 5  filtrate,   as described  in  Section
 7.3.2 below.  Discard  the filter.

 7.3.2     Container No. 1 (Impingers, Probe, and Filter Holder) and, if Applicable,  No.
 1A (HCl Rinse)—Filter  the  contents  of Container No. 1 through Whatman 40  filter paper
 into a 1-L volumetric flask to remove the brown MnO_ precipitate.   Save  the  filter.
'Add the sample filtrate  from Container No. 3 to the 1-L  volumetric flask and dilute to
 volume with water.   If  the  combined filtrates are  greater than 1000  mL, determine the
 volume to the nearest mL and make the appropriate  corrections for blank subtractions.
 Mix thoroughly.
          Mark the filtrate as  Analysis  Sample  No.  A.I  and analyze  for Hg within  48 h
 after completing the filtration step.  Place the saved filter, which was used to remove
 the brown MnO: precipitate, into a  container of  appropriate size. Add 25 mL of £ N HCl
o
 o
 o

-------
                                                            Section No. 3.19.10
                                                            Date  September 21, 1992
                                                            Page  11

 to the filter and allow the filter, with its brown residue, to digest for a minimum of
 24 h at room temperature.  Filter the contents of Container No.  1A through a  Whatman
 40 filter paper  into a 500-mL volumetric flask.  Then filter the digestion of  the brown
 MnO;  precipitate from Container No.  1  and  the Whatman paper  filter into the  500-mL
 volumetric flask.  Dilute to volume with water.  Mark this 500-mL dilute  solution as
'Analysis Sample No. HCl  A.2 and analyze for Hg.  Discard the  filters.

 7.3.3     Containers No. 5 (Absorbing Solution Blank) and No. 6 (HCl Rinse Blank)—Treat
 Container No. 5 the same as Container No.  1, described in the previous  section.   Add
 the filter blank filtrate from  Container No. 4 to the 1-L volumetric  flask and dilute
 to volume.   Mix thoroughly.   Mark this as Sample  No.  A.I  blank and analyze  for Hg
 within 48  h after completing  the filtration  step.   Digest any brown  precipitate
 remaining on the filter from the filtration of Container No.  5,  using  the procedure
 described in Section 7.3.2.   Filter the contents of Container No. 6 using the procedure
 described in  Section  7.3.2 and combine  into  the   500-mL volumetric  flask  with  the
 filtrate from the digested blank MNO2 precipitate.  Mark this resultant 500-mL combined
 dilute solution as Analysis  Sample No. HCl A.2 blank.   Note:  When analyzing blank
 samples A.I blank  and HCl  A.2  blank, always begin with 10-mL  aliquots.   This note
 applies specifically  to  blank samples.
                                                --*"""
 7.4        Analysis                                .

 7.4.1      Calibrate the  spectrophotometer and recorder  and prepare  the  calibration
 curve  as  described in sections  8.1 and  8.2.   Then  repeat  the  procedure  used to
 establish the calibration curve with  aliquots of appropriate size (1  to 10 mL)  of  the
 samples (from sections 7.3.2 and 7.3.3) until two consecutive peak heights agree within
 3% of  their  average value.   If  the  10-mL sample is  below the detectable limit, use a
 larger aliquot (up  to  20  mL), but  decrease  the volume  of water added to the aeration
 cell  accordingly to prevent  the solution  volume from exceeding the capacity  of  the
 aeration  bottle.  If  the  peak maximum of a  1-mL aliquot  is off scale,  further dilute
 the original sample to bring the Hg concentration  into  the calibration range  of  the
 spectrophotometer.  If the  Hg content of the absorbing  solution  and filter blank is
 below  the working range  of  the  analytical method, use  zero for the blank.

 7.4.2      Run  a  blank and standard at  least after  every five  samples to check  the
 spectrophotometer calibration;  recalibrate as necessary.  It also is  recommended that
 at least one sample  from  each  stack  test be checked by the Method of Standard Additions
 to confirm that  matrix effects  have not interfered  with  the analysis.

 8.0       Calibration and Standards

          The  calibration and  standards are the  same as in  Method  101,  Section 8,
 except  for the following  variations:

 8.1       Optical Cell Heating  System Calibration

          Same as in Method  101, Section 8.2, but use a 25-mL graduated cylinder to  add
 25 mL  of  water to the  bottle  section  of  the aeration cell.
                                                                                  i,
 8.2       Spectrophotometer and Recorder Calibration

 8.2.1     The Hg response may be measured by either peak height or peak area.  Note:
The temperature  of  t,he solution affects the rate  at which elemental Hg is released;

-------
                                                            Section No. 3.19.10
                                                            Date September 21, 1992
                                                            Page 12

consequently, it  affects  the shape of the absorption curve  (area)  and the point of
maximum absorbance (peak height).  To obtain  reproducible results, all solutions must
be brought to room temperature before use.

8.2.2     Set the  spectrophotometer wave  length  at 253.7 nm  and 'make  certain the
optical cell is at the minimum temperature that will prevent water condensation. Then
set the recorder  scale as follows:  Using a 25-mL graduated cylinder,  add 25 mL of
water to the aeration cell bottle,  and pipet  5 mL  of the working Hg standard solution
into the aeration cell.  Note: Always add the Hg-containing solution to the aeration
cell after the 25 mL of water.

8.2.3     Place a Teflon-coated stirring bar in  the  bottle.  Add 5 mL of  the 4%  KMn04
to the aeration bottle and mix well.  Attach the  bottle section  to the bubbler section
of the  aeration  cell.  Make  certain  that:  (1)  the aeration cell  exit arm stopcock
(Figure 101-3 of  Method 101) is closed  (so  that  Hg will not  prematurely  enter the
optical cell when the reducing agent is being added); and (2) there is no flow through
the bubbler.  Add 5 mL of  sodium chloride hydroxylamine in 1-mL increments until the
solution  is  colorless.  Now  add 5 mL of  tin  (II)  solution to  the  aeration  bottle
through the side arm and immediately stopper the side arm.   Stir the solution for 15
s, turn on  the  recorder,  open the  aeration  cell" exit  arm  stopcock,  and immediately
initiate aeration with continued stirring.   Determine  the  maximum absorbance  of the
standard,  and set this value  to read 90% of the recorder full scale.
          Before uao, clean nil glao8wa.ro, both now and unod,  as follows: Brush with
soap and tap water, liberally rinse with  tap water, soak for 1 h In 50% HNO3.   Rinse
with dolonlzod distilled water.

6.1       Flow Calibration

          Assemble the aeration system an  shown  in Figure 101-5.   Sot  the  outlet
pressure on the aeration gas cylinder regulator to a minimum pressure of 500 mm Hg (10
pel), and use  the flow motoring valve and a bubble flow meter or wot-tost meter to
obtain  a  flow rate of 1.5 ± 0.1  L/mln  through the aeration cell.  After the flow
calibration IB completed,  remove the bubble flow noter from the system.

8.2       Optical Cell Heating System_ Calibration

          Using a 25-mL Graduated  cylinder/ add 25 mL of water to the bottle  section
of the aeration cell  and attach  the bottle section to the bubbler section of the  cell.
Attach  the aeration coll  to  the optical coll; while aerating at 1.5 L/nln, determine
tho minimum variable  transformer sotting necessary to prevent condensation of moisture
In the optical cell and In the connecting tubing.   (This setting should not exceed 20
volts.)

8.3       Spectrophotometer and Recorder  Calibration

8.3.1     The Hg response may bo measured by either peak height or peafc area.   fWote:
The temperature of the solution affects the rate  at which elemental Hg ID released;
conse
-------
                                                            Section No. 3.19.10
                                                            Date September 21, 1952
                                                            Page 13

 Bet the recorder scale as follows.-   Using a. 25-mL Graduated cylinder, add 25 mL  of
 water to the aeration cell bottle and pipet 5 aL of the working Hg standard  solution
 into the aeration cell.   (Note: Always add the Hg-containing solution  to the  aeration
 cell after the 25 mL of water.)

 8.3.3     Place  a Teflon-coated  stirring bar in  the bottle.   Using a  25-mL graduated
 cylinder,  add 25 mL of laboratory pure water to  the aeration  cell  bottle.  Pipet 5.0
 mL of the  working Hg standard solution to the aeration cell.   Add 5 mL of the 4% KMnO,
 absorbing solution,  followed by  5 mL of 15% UNO, and 5 mL of 5% KMnO<  to the  aeration
 cell,  and mix well  using a swirling motion.  Attach the bottle to  the  aerator, making
 sure that:  (1)  the  exit  arm stopcock  is closed,  and  (2) there  is  no aeration gas
 flowing through the  bubbler.    Through  the side  arm,  add 5 mL  of  sodium  chloride
 hydroxylamine solution in 1 mL-increments until the solution is colorless.   Through the
 side arm,  add 5 mL of  the Tin  (II)  reducing agent to the aeration cell bottle, and
 immediately stopper the side arm.  Stir the solution for  15 s and turn  on the  recorder
 or integrator.   Open the aeration cell exit arm stopcock and initiate the gas flow.
 Determine  the maximum height (absorbance) of the standard,  and set  this value to read
 90% of the recorder full  scale.

 8.4       Calibration Curve                    -->-

 8.4.1     After  setting the recorder scale, repeat the procedure in Section 8.3 using
  -,  1-,  2~,  3-,  4-, and 5-mL aliquots of the working standard solution (final amount
 f Kg In  the  aeration  cell  Is  0,  200,  400, 600,  BOO,  and  1000  ng,  respectively).
 Repeat  this procedure on each aliquot size until  two consecutive peaks  agree within  3%
 of their average value.  (Note: To prevent Hg carryover from one sample to  another,  do
 not  close  the aeration cell from the optical cell until the recorder pen has  returned
 to the  baseline.)

 8.4.2     It should not be necessary to disconnect the aeration gas inlet line  from the
 aeration cell when changing samples. After separating the bottle and .bubbler  sections
 of the  aeration cell,  place the bubbler  section into a  600-mL beaker containing
 approximately 400 mL of water.   Rinse the bottle section of the aeration  cell with a
 stream  of water to remove all traces of the tin (II) reducing agent. Also, to prevent
 the loss of Hg before aeration, remove all traces of the reducing agent  between samples
 by washing with water.  It will be necessary, however, to wash the  aeration cell parts
 with  concentrated  HCl if any  of  the following conditions occur:  (1)  a  white film
 appears on any inside surface of the aeration cell; (2)  the calibration curve changes
 suddenly;  or (3) the replicate samples do not yield reproducible results.

 8.4.3     subtract  the  average   peak height  (or  peak area)  of the blank  (0-aL
 aliquot)-which should be  less  than 2% of" recorder  full  scale-from the averaged peak
 heights  of the 1-,  2-,  3-, 4-, and 5-mL aliquot standards.  If the  blank absorbance  is
 greater than 2% of full-scale,  the probable cause is Hg contamination  of a reagent  or
 carry-over  of Hg from  a  previous sample.   Plot the corrected peak  height  of each
 standard solution versus the corresponding final total Hg weight in the aeration cell
 (in ng), and draw the best-fit straight line.  This line should either pass  through the
 >rigin  or pass through a point no further from the origin  than  * 2 %  of the  recorder
 ull scale.  If  the line does not  pass through or very near to  the origin, check for
"nonlinearity of  the curve and for incorrectly prepared  standards.

 9.0       Calculations

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                                                            Section No.  3.19.10
                                                            Date September  21,  1552
                                                            Page 14

9.1       Dry-Gas  Volume,  Volume  of  Water Vapor  and Moisture  Content,  Stack-S=!
Velocity, Isokinetic Variation and Acceptable Results, and Determination of Compliance

          Same as in Method  101, Sections 9.1, 9.2,  9.3, 9.6, and  9.7,  respectively,
but use data obtained  from this  test.

9.1       Dry-Gas Volume

          Using the data from this toot/  calculate  Vflttll), the dry-gas sample  volume at
standard conditions  (corrected for leakage, if necessary) as outlined in Section 6.3
of Method 5.                                                       '

9.2       Volume of Water Vapor  and Moisture Content

          Using the data obtained from this tost,  calculate  the  volume of water vapor
Vul,ca,  and the moisture content Bw,  of  the stack-gas.   Use  equations  5-2 and  5-3  of
Method 5.

9.3       Stack-Gas Velocity
                                                -•*"""
          Using the data from this teat  and Equation 2-9 of Method 2,  calculate the
average stack-gas velocity v,.

9.4       Isokinetic Variation and Acceptable Kesults   '     •                 ;  "

          Same as in Method  5, Sections  6.11 and 6.12,  respectively.

9.5       Determining  Compliance

          Each performance test  consiots of three  repetitions of the  applicable tesc
.method.  For the purpose of determining compliance with an applicable national emission
standard, use the average of the results of all repetitions.

9.2       Total Mercury

          For each source sample,  correct the average maximum absorbance of  the tvrc
consecutive  samples  whose peak  heights  agreed within  3%  of their  average  for the
contribution of the blank.   Then calculate the total Kg content  in  |Jg in each sample.
Correct  for any dilutions made  to bring  the  sample into  the  working range  of th<=
spectrophotometer.
O
 O

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                                                             Section -No;  3.15.10
                                                             Date September 21,  1952
                                                             Page 15
                          [C(HC1 Jb-Z *)•„;, DFt:.K]
                         ~~~
                                    Equation  101A-1
 where:
          m(HCl)H,
          C(HC1),
          C(HC1 blk)H,
          DF
          DFM,




          V(IH.:


          10"

          S
Total  blank corrected ng  of  Hg in  HC1  rinse  and HC1
digestate of filter sample. ...

Total  ng of Hg  analyzed ;in.^the  aliquot  from the BOO-iri
Analysis Sample No. HCLA.2.,

Total  ng of Hg  analyzed .in aliquot of the  500-rnL Anal-
ysis Sample No. HC1_A.2 blank.

Dilution  factor  for   the   HC1  digested  Hg-ccntaining
solution, Analysis  Sample  No.  HC1  A.2.   This  dilution
factor  (DF)  applies only to the intermediate  dilution
steps  because the  original sample  volume (V.),.-: of HCi
A.2 has  been  factored out   in the equation,  along with
the sample  aliquot,  (S) .    In Equation 6.9,  the sample
aliquot, S,  is introduced  directly  into the  aeration
cell for analysis  according to the procedure outlined in
Section 3.19.5.3.4.  A dilution factor is required only
if it is necessary to  bring the sample into the analyti-
cal instrument's calibration range.   If  no  dilution is
necessary,  then DF equals  1.0.

Dilution factor for  the  Analysis  Sample  No.   HCI A. 2
blank.  (Note: Normal  dilution factor calculations apply
here.)

Solution volume of  original sample,  500  mL  for samples
diluted as described  in Section 7.3.1.

Conversion factor, Jlg/ng.

Aliquot volume of sample added to aeration cell,  mL.

Aliquot volume of blank added to aeration cell, ~iL.
          Note: The maximum allowable blank  subtraction  fcr the HCI  is  the  lesser cf
the two following values:  (1)  the actual  blank measured value (Analysis Sample I'io. HCI
 .2 blank); or (2) 5% of the Hg content in the combined HCI rinse  and digesced sampi*
'(Analysis Sample No. HCI A.2).
where:

-------
                                                            Section No.  3.19.10
                                                            Date September  21,  199
                                                            Page 16
                                                                           o
                                             DF
                        (C(fltrblk)   DFblk
          m(fltr).
          C(fltr)
          C(fltr blk).
          V
           f ibH.i
                                                          10~?    Equation  101A-2
                                      Jblk
                 =   Total blank corrected Hg of Hg  in KMNO4 filtrate and HNC;
                    digestion  of  filter  sample.

                 =   Total  ng of  Hg  in aliquot of  KMNO4  filtrate  and HNC-.
                    digestion of filter analyzed (aliquot of Analysis Sample
                    No.  A.1).

                 =   Total ng of Hg in aliquot of KMNO< blank and HNO3  diges-
                    tion of  blank  filter  analyzed  (aliquot  of  Analysis
                    Sample No. A.I blank).

                 =   Solution volume of Original sample, normally 1000 mL fcr
                    samples diluted  as described in Section "7.3.2.

                 =   Solution  volume  of  blank  sample,  1000 mL for  samples
                    diluted as described in Section 7.3.2
          Note: The maximum allowable blank subtraction for the HC1 is  the  lesser cf
the two following values:  (1) the actual blank measured value  (Analysis Sample No. A.I
blank); or  (2) 5% of the Hg content in the filtrate (Analysis Sample No.  A.I).
O
                                = m(HCl}H. + m(fltr)H
                                                       Equation  101A-3
where:
9.3
          m(fltr)H,
            =  Total blank corrected Hg content in each sample,  \ig.

            =  Total blank corrected ug of Hg in HCl rinse and HCl digestate
               of filter sample.

            =  Total blank  corrected Hg of Hg  in KMNO,.  filtrate ar.c  HNC:.
               digestion of filter sample.
Mercury Emission Rate
          Calculate the Hg emission rate  R  in  g/day for continuous operations using
Equation 101A-4.  For  cyclic  operations,  use only  the  time per day each stack is ir.
operation.  The total Hg emission rate from  a source will be the summation of results
from all stacks.                                                                  <• .

v;here:
                                                                            O
                      Total blank corrected Hg content in each sample,  ug.

-------
A.


86,400


10'"
T.


Ps


K
                                                   Section No.  3.19.10
                                                   Date  September 21,  1992
                                                   Page  17
                 R = K
                         Ha Vs Ar (86,400 X
                         V     + V     I  ( T IP )
                         "mlred!    VK,£iJ\ -I  v •'-' cf'


            Average  stack-gas velocity,  m/sec (fps).


            Stack  cross-sectional  area,  nr  (ft*).


            Conversion  factor,  s/day.


            Conversion  factor,
                                                        Equation 101A-4
            Dry-gas  sample volume  at standard  conditions,  corrected  for
            leakage  (if any), nr (ftj).


            Volume of water vapor at  standard conditions, m3 (ft3) .


            Absolute stack-gas  temperature, °K  (°R).


            Absolute stack-gas  pressure" mm Hg  (in. Hg) .


            0.3858 °K/mm Hg for metric units.


            17.64 °R/in. Hg for English units.

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                                                            Section No.  3.19.10
                                     	                  Date September 21.  1992
                                                            Page 18

10.1      Biblioqraphy

          1.       Same as bibliography  in Method  101.

          2.       Mitchell,  W.J.,  M.R. Midgett,  J.C,  Suggs,  and  D.  Albrinck. Tesz
                  Methods to Determine the Mercury Emissions from Sludge Incineraticn
                  Plants.   EPA-600/4-79-058.   September  1979.   U.S.   Environmental
                  Protection Agency  (EPA).  Research  Triangle Park,  NC.

          3.    '   Wilshire,  Frank W.,  J.E.  Knoll,  T.E/ Ward,  and  M.R.  Midgett.
                  Reliability Study of  the  U.S. EPA's Method 101A - Determination of
                  Particulate and Gaseous Mercury Emissions. Report No.  600/D-31/21&
                  AREAL 367, NTIS Ace No. PB91-233361. U.S. Environmental Protectior.
                  Agency  (EPA). Research  Triangle  Park, NC.
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                                                               Section No.3.19.11
                                                               Date September 3,  1952
                                                               Page 1
 11.0      REFERENCES

 1.        Method 101A - Determination of Particulate and Gaseous Mercury Emissions from
          Sewage Sludge Incinerators. Federal Register, Volume  47,  July 8, 1982,  p.
          24703.

 2.        Corrections to Method 101A-, Federal Register,  Volume ,49,  September 12,  1984,
          p.  35768.

 3.        Corrections to Method 101A. Federal Register,  Volume 53,  September 23,  1988,
          p.  36972.             ,           .

 4.        Method 101 - Determination of Particulate and  Gaseous Mercury Emissions from
          Chlor-Alkali  Plants - Air Streams. Federal Register, Volume 38, May 6,  1973,
          p.  08826.

 5.        Amendments  to Method .101.  Federal Register,  Volume 47, July 8,  1982,  p.
          24703.
6.
8.
Corrections  to Method  101. Federal Register, Volume  49, September  12,  1984,
p.  35768.

Corrections  to Method  101. Federal Register, Volume  53, September  23,  1988,
p.  36972.                                             '  "' '

Wilshire,  Frank  W., J.E. Knoll,  T.E. Ward, and  M.R. Midgett. Reliability
Study  of the  U.S.  EPA's Method 101A  -  Determination of  Particulate .and
Gaseous  Mercury  Emissions. Report No. 600/D-31/219 AREAL 367, NTIS Ace No.
PE91-233361, U.S. Environmental  Protection Agency, Research Triangle  Park,
NC.                               .. " . .
9.       Addendum  to  Specifications for Incinerator  Testing at Federal Facilities.
         PHS, NCAPC. December 6, 1967.

10.      Determining Dust Concentration  in a Gas Stream. ASME Performance Test  Code
         No. 27. New York, NY. 1957.
11.
12.
13.
DeVorkin, Howard, et al. Air Pollution Source Testing Manual. Air  Pollution
Control District. Los Angeles, CA. November 1963.                       -:

Hatch,  W.R.,  and W.I.  Ott. Determination  of  Sub-Microgram Quantities  of
Mercury by Atomic Absorption Spectrophotometry. Anal. Chem. 40:2085-87,  1968.

Mark, L.S.  Mechanical  Engineers' Handbook. McGraw-Hill  Book Co.,  Inc.  New
York, NY. 1951.

Martin,   Robert  M.   Construction  Details  of  Isokinetic  Source  Sampli'ng
Equipment.  EPA APTD-0581,  U.S.  Environmental  Protection Agency.  Research
Triangle Park, NC. April 1971.                                         :'y

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                                                              Section No.3.19.11
                                                              Date September  3,  1992
                                                              Page 2

 15.      Western   Precipitation   Division   of  Joy  Manufacturing  Co.   Methods  for
         Determination of Velocity, Volume, Dust and Mist Content of Gases. Bulletin
         WP-50. Los Angeles,  CA.  1968.

 16.      Perry,  J.H.  Chemical Engineers'  Handbook.  McGraw-Hill Book Co.,  Inc.  New
         York, NY. 1960.

 17.      Rom, Jerome J. Maintenance, Calibration, and Operation of Isokinetic Source
         Sampling  Equipment.  EPA  APTD-0576,  U.S.  Environmental  Protection Agency-
         Research Triangle Park, NC. April  1972.

 18.      Shigehara, R.T., W.F. Todd, and W.S. Smith. Significance of Errors in Stack
         Sampling Measurements. Stack Sampling News. 1{3):6-18,  September 1973.

 19.      Smith, W.S.,  et al.  Stack Gas Sampling  Improved  and Simplified  with  New
         Equipment. APCA Paper No. 67-119.  1967.

 20.      Smith, W.S., R.T. Shigehara, and  W.F.  Todd.  A Method of Interpreting Stack
         Sampling Data. Stack Sampling News. 1(2):8-17, August 1973.

 21.      Specifications  for  Incinerator Testing at Federal Facilities.  PHS,  NCAPA.
         1967.

 22.      Standard Method for Sampling Stacks for Particulate Matter.  In: 1971 Annual  F   j
         Book of ASTM Standards, Part 23. ASTM Designation D 2928-71. Philadelphia, PA  ^—'
         1971.

 23.      Vennard,  J.K.  Elementary  Fluid  Mechanics. John Wiley and Sons, Inc. New York.
         1947.

 24.      Mitchell, W.J.,  and M.R.  Midgett.  Improved Procedure  for Determining Mercury
         Emissions from Mercury Cell Chlor-Alkali  Plants. J.  APCA.  26:674-677, July
         1976.

25.      Shigehara, R.T. Adjustments  in the EPA Nomograph for  Different  Pitot Tube
         Coefficients and Dry Molecular Weights.  Stack Sampling News. 2:4-11, October
         1974.

26.      Vollaro,  R.F. Recommended Procedure for Sample  Traverses  in  Ducts Smaller
         than 12 Inches  in Diameter.  U.S.  Environmental Protection Agency, Emission
         Measurement Branch. Research Triangle Park, NC. November 1976.

27.      Klein, R., and C. Hach. Standard Additions: Uses and Limitation in Spectro-
         photometric Measurements. Amer. Lab. 9:21, 1977.
28.      Water, Atmospheric Analysis. In:  Annual Book of ASTM Standards, Part 31. ASTM
         Designation D 1193-74. Philadelphia, PA. 1974.

29.      Mitchell, W.J., M.R. Midgett,  J.C.  Suggs,  and D.  Albrinck. Test Methods to
         Determine the  Mercury  Emissions from Sludge  Incineration Plants.  EPA-600-
         /4-79-058,  U.S. Environmental Protection Agency. Research  Triangle Park, NC.
         September 1979.
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