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  ~              US ENVIRONMENTAL PROTECTION AGENCY
Q. • ^f ^M^J!f%  OFFICE OF AIR QUALITY PLANNING AND STANDARDS
0> I Inr^^lJ^^ STATIONARY SOURCE COMPLIANCE DIVISION
                 WASHINGTON, DC 20460

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                                   EPA-340/1 -84-001 a
VOC  Sampling and Analysis Workshop
   Volume  I. VOC Reference Methods
                       Prepared by

                   PEDCo Environmental, Inc.
                     11499 Chester Road
                     Post Office Box 46100
                   Cincinnati, Ohio 45246-0100
                       Prepared for

              U.S. ENVIRONMENTAL PROTECTION AGENCY
              Office of Air Quality Planning and Standards
                Stationary Source Compliance Division
                    Washington, D.C. 20460

                      September 1983

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                             INTENDED PURPOSE
     This is not an official policy and standards document.  The opinions,
findings, and conclusions are those of the authors and not necessarily those
of the Environmental Protection Agency.  Every attempt has been made to repre-
sent the present state of the art as well as subject areas still under eval-
uation.  Many of the VOC methods contained in this manual are either draft
methods or guideline procedures.  Since any draft method is subject to change
and even elimination, none of the material presented should be used as an EPA
policy or recommendation unless it is a promulgated EPA reference method.  The
methods are included as training material only.  Any mention of products or
organizations does not constitute endorsement by the Unites States Environmental
Protection Agency.

     This document is issued by the Stationary Source Compliance Division,
Office of Air Quality Planning and Standards, USEPA.  It is for use in work-
shops presented by Agency staff and others receiving contractual or grant
support from the USEPA.  It is part of a series of instructional manuals
addressing VOC compliance testing procedures.

     Governmental air pollution control agencies establishing training pro-
grams may receive single copies of this document, free of charge, from the
Stationary Source Compliance Division Workshop Coordinator, USEPA, MD-7,
Research Triangle Park, NC 27711.  Since the document is specially designed
to be used in conjunction with other training materials and will be updated
and revised as needed periodically, it is not issued as an EPA publication
nor copies maintained for public distribution.

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                                 CONTENTS
40 CFR PART 60 - APPENDIX A - REFERENCE TEST METHODS

     Method 1A.  Sample and Velocity Traverses for Stationary
       Sources with Small Stacks or Ducts (proposed 48 FR 48955,
       10-21-83)                                                      1A-1
                               ^
     Method 2A.  Direct Measurement of Gas Volume Through Pipes
       and Small Ducts (promulgated 48 FR 37592, 8-18-83)             2A-1

     Method 2B.  Determination of Exhaust Gas Volume Flow Rate
       from Gasoline Vapor Incinerators (promulgated 48 FR 37594,
       8-18-83)                                                       2B-1

     Method 2C.  Determination of Stack Gas Velocity and Volumetric
       Flow Rate from Small Stacks and Ducts--Standard Pitot Tube
       (proposed 48 FR 48956, 10-21-83)                               2C-1

     Method 18.  Measurement of Gaseous Organic Compound Emissions
       by Gas Chromatography (promulgated 48 FR 48344, 10-18-83)      18-1

     Method 21.  Determination of Volatile Organic Compound Leaks
       (promulgated 48 FR 37598, 8-18-83)                             21-1

     Method 23.  Determination of Halogenated Organics from
       Stationary Sources  (proposed 45 FR 38766, 6-11-80)             23-1

     Method 24.  Determination of Volatile Matter Content, Water
       Content, Density, Volume Solids, and Weight Solids of
       Surface Coatings  (promulgated 45 FR 65958, 10-3-80)            24-1

     Method 24A. Determination of Volatile Matter Content and
       Density of Printing Inks and Related Coatings (promulgated
       47 FR 50655, 11-8-82)                                         24A-1

     Method 25.  Determination of Total Gaseous Nonmethane Organic
       Emissions as Carbon (promulgated 45 FR 65959, 10-3-80)         25-1

     Method 25A. Determination of Total Gaseous Organic Concen-
       tration Using a Flame lonization Analyzer (promulgated
       48 FR 37595, 8-18-83)                                         25A-1

     Method 25B. Determination of Total Gaseous Organic Concen-
       tration Using a Nondispersive Infrared Analyzer (promul-
       gated 48 FR 37597, 8-18-83)                                   25B-1

     Method 27.  Determination of Vapor Tightness of Gasoline
       Delivery Tank Using Pressure-Vacuum Test (promulgated
       48 FR 37597, 8-18-83)                                          27-1

                                    i 1 i

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                           CONTENTS (continued)
40 CFR PART 61 - Appendix B - REFERENCE TEST METHODS

     Method 106.  Determination of Vinyl Chloride from
       Stationary Sources (promulgated 47 FR 39170, 9-7-82)

     Method 107.  Determination of Vinyl Chloride Content of
       Inprocess Wastewater Samples and Vinyl Chloride Content
       of Polyvinyl  Chloride Resin, Slurry, Wet Cake, and Latex
       Samples (promulgated 47 FR 39174, 9-7-82)

     Method 110.  Determination of Benzene from Stationary
       Sources (proposed 45 FR 26660, 4-18-80; updated 7-23-82)

40 CFR PART 61 - APPENDIX C - QUALITY ASSURANCE PROCEDURES

     Procedure 1.  Determination of Adequate Chromatographic Peak
       Resolution (promulgated 47 FR 39176, 9-7-82)

     Procedure 2.  Procedure for Field Auditing GC Analysis
       (promulgated 47 FR 39179, 9-7-82)

APPLICABLE STANDARDS TEST METHODS

     ASTM-D1475-60.   Density of Paint, Varnish, Lacquer, and
       Related Products

     ASTM-D2369-81.   Volatile Content of Coatings

     ASTM-D3792-79.   Water Content of Water-Reducible Paints
       by Direct Injection into a Gas Chromatograph

     ASTM-D4017-81.   Water in Paints and Paint Materials by
       the Karl Fischer Method
                                                                      Page
  106-1
  107-1


  110-1
   Pl-1


   P2-1
D1475-1

D2369-1


D3792-1


D4017-1
                                     IV

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     METHOD 1A - SAMPLE AND VELOCITY TRAVERSES FOR STATIONARY SOURCES WITH
                            SMALL STACKS OR DUCTS              DRAFT
1.  Applicability and Principle                      DO NOT QUOTE OR CITE
     The applicability and principle of this method are identical  to Method 1,
except its applicability is limited to stacks or ducts less than about 0.30
                                      2         2
meter (12 in.) in diameter, or 0.071 m  (113 in. ) in cross-sectional area,
but equal to or greater than about 0.10 meter (4 in.) in diameter, or 0.0081
 2           2
m  (12.57 in. ) in cross-sectional area.
     In these small diameter stacks or ducts the conventional pitobe assembly
(consisting of a Type S pitot tube attached to a sampling probe, equipped with
a nozzle and thermocouple) blocks a significant cross-section of the duct and
prevents a true traverse.  Therefore, for particulate sampling in small stacks
or ducts, the gas  velocity is measured using a standard pitot tube downstream
of the actual emission  testing site.  The straight run of duct between the
sampling and velocity measurement sites allows the flow profile, temporarily
disturbed by the presence of the sampling probe, to redevelop and stabilize.
     The cross-sectional layout and location of  traverse points and  the
verification of the  absence of cyclonic flow are the same as in Method 1,
Sections 2.3 and 2.4, respectively.   Differences from Method 1, except as
noted, are given below.
2.   Procedure
     2.1  Selection of Measurement  Site.
     2.1.1   Particulate  Traverses  - Steady  or  Unsteady  Flow.  Select  a particulate
measurement site located preferably at least  eight equivalent  stack  or
duct diameters downstream and  ten equivalent  diameters  upstream from
any flow disturbance such  as  a bend,  expansion,  or contraction  in  the  stack,
                                     1A-1

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or from a visible flame.  Locate the velocity measurement site 8 equivalent
diameters downstream of the particulate measurement site.  See Figure
1A-1.  If such locations are not available, select an alternative particulate
measurement location at least two equivalent stack or duct diameters
downstream and two and one-half diameters upstream from any flow disturbance.
Locate the velocity measurement site 2 equivalent diameters downstream from
the particulate measurement site.  (See Section 2.1 of Method 1 for
calculating equivalent diameters for a rectangular cross-section.)
     2.1.2  Particulate (Steady Flow) or Velocity (Steady or Unsteady Flow)
Measurements.  If the average total volumetric flow rate in a duct is constant
with respect to time or if only velocity measurements are required use the
same criterion as in Section 2.1 of Method 1.
     2.2  Determining the Number of Traverse Points.
     2.2.1  Particulate Measurements (Steady or Unsteady Flow).  Use Figure
1A-2 to determine the number of traverse points.  Before referring to the
figure, however, determine the distance between the velocity and sampling sites
and the distances to the nearest upstream and downstream disturbances and
divide each distance by the stack diameter or equivalent diameter to determine
the distances in terms of the number of duct diameters.  Then, determine the
number of traverse points from Figure 1A-2 corresponding to each of
these three distances.  Choose the highest of the three numbers of
traverse points (or a greater number) so that for circular ducts the
                                                     •
number is a multiple of 4; for rectangular ducts use one of those numbers
shown in Table 1-1 of Method 1.
     2.2.2  Particulate (Steady Flow) and Velocity (Non-Particulate) Measurements.
Use Figure 1A-3 to determine number of traverse points, following the same
procedure used for particulate traverses as described in  Section 2.2.1 of
Method 1.
                                     1A-2

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3.  Bibliography
     1.  Same as Method 1, Section 3, Citations 1 through 6.
     2.  Vollaro, Robert 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.  January 1977.
                                    1A-3

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            RECOMMENDED SAMPLING ARRANGEMENT
                      FOR SMALL DUCTS
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       MINIMUM NUMBER OF TRAVERSE POINTS FOR

        VELOCITY (NONPARTICULATE) TRAVERSE
      50
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DUCT DIAMETERS UPSTREAM FROM DISTURBANCE (DISTANCE A)


  1.0          1.5          2.0
                                                    2.5
11)11 II
* HIGHER NUMBER IS FOR RECTANGULAR
STACKS OF DUCTS



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                                             10

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MINIMUM NUMBER OF TRAVERSE POINTS

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      DUCT DIAMETERS UPSTREAM FROM DISTURBANCE (DISTANCE A)

        1.0          1.5           2.0          2.5
1 1 1 1 	 1 	 1 	 1 	
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                         5      6      7      8


             DUCT DIAMETERS DOWNSTREAM FROM FLOW DISTURBANCE (DISTANCE B)
                                            10

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Federal Register /  Vol. 48, No. 205 / Friday, October 21, 1983 / Proposed Rules          48955
                                                                    (Sec. 114 of the Clean Air Act as amended (42
                                                                    U.S.C. 7414)]

                                                                       It is proposed that Appendix A of 40
                                                                    CFR Part 60 be amended as follows:
                                                                       2. Reference Method 1A is added to
                                                                    Appendix A as follows:
                                                                    Method 1A—Sample and Velocity Traverses '
                                                                    for Stationary Sources with Small Stacks or
                                                                    Ducts
                                                                    1. Applicability and Principle
                                                                      The applicability and principle of this
                                                                    .method are Identical to Method 1. except its
                                                                    applicability is limited'to stacks-or ducts less
                                                                    than about 0.30 meter (12 in.) in diameter, or
                                                                    QJE/n m* (113 in.1) in crass-sectional area, but
                                                                    equal to or greater than about 0.10 meter (4
                                                                    in.) in diameteri or 00)081 m1 (12.57 in.} in
                                                                    cross-sectional area.
                                                                       In these smalt diameter stacks or ducts the
                                                                    ' conventional pilot assembly (consisting of a
                                                                    Type S pitot tube attached to a sampling
                                                                    probe, equipped with a nozzle and
                                                                    thermocouple) blocks a significant cross-.
                                                                    * MA«^X«^B Jtf itlj- ^iMMA MMjt «M^h^^M*AM A 4w^A
                                                                     SBEuun in iDB HOCK ami promts •-WHS •
                                                                     treverse. Therefore, forpaiUiulate sampling
                                                                     in small stacks or ducts, the gas velocity h.
                                                                     measmwlvsing a standard pitnt-tDM
                                                                     uuwnateeajs of that aytnal ennssion tasting
                                                                     site. The atnight ran of dnct between tfaa
                                                                     inmnling and. velocity measurement sites  •
                                                                     allows the flow profile, temporarily disturbed
                                                                     by the" presence of the sampling probe, to
                                                                     redevelop and etahilrra ,
                                                                       The cross-sectional iayoat and location of
                                                                     traverse points and the verification ol n»-
                                                                     absence of cyclonic flow are the same asm
                                                                     Method t' Sections 23 and Z4. respectively.
                                                                     Digerence»from Method X except as noted.
                                                                     are given below.
                                                                       « SetocSon of Measurement Sits.
                                                                       2.1J.  ParticaUteMeasuienKiirts  Steady
                                                                     or Umrteady Flow. Select a paniculate
                                                                     nwasonment site locaied preferably at least
                                                                     eight cojnValent stack of UijfalnlaiiiBtiits
                                                                     jjffyjMtnuiiii jnd in aqnivalant diamgtera
                                                                     upstream from any flow disturbances such as
                                                                     a bgndti expansions, or coatntctiona in^the
                                                                     stack, or from « visible flame. Next, locate
                                                                      eouivalent diameters downstream of the
                                                                      paroculate measurement site. See Figure 1A-
                                                                      l.If such locations are not available, select
                                                                      an alternative particulate measurement
                                                                      location at least two equivalent stack or duct
                                                                      diameters downstream and two and one-half
                                                                      diameters upstream from any flow .
                                                                      disturbance. Then, locate the velocity
                                                                      measurement site two equivalent diameters
                                                                      downstream from the particulate     -   . -
                                                                      measurement site. (See Section Zl of Method
                                                                      1 for calculating equivalenldiameters for a
                                                                      rectangular cross-section.)
                                                 1A-7

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                           Figure  1A-1.   Recoomended sampling arrangement for  small ducts.
        Parfculate (Steady Flow) or Velocity
(Steady or Unsteady Flow) Measurements. If
the aveiajfs total volumetric flow rate in •
duel fa constant with respect to tone or if
only Telocity measurements are required use
the same criterion as in Section 24 of Method
t..         '  .        -      --.•••'•
Points..
  2£1.  ParnculateMeasnrements(Steaayor
Unsteady Flow). Use Figure 1-1 of Method 1
m iM»nii aipifaabirf «tiam«l»r f«

luuuoar of uucl dtametetSa Thent delaruuna
the number of traverse points from Figure M
of Method 1 corresponding to each of these
threeAstanees. Choose the highest of the
three niiinhafa of tra.vgrinf'pofarti: (or a greater
number) so that Cor circular ducts the number
is a multiple of Soon for nctangolar ducts use
one of those nnmbers shown in Table U of
Methodl,
                                                  Pardculate (Steady Flow) and
                                          Velodtr (Non-ParticuUte) Measurements.
                                          Use Figure lA^a to determine number of
                                          traverse points, following die same procedure
                                          used far parUculate traverses as described in
                                          - Section 223. of Method 1.
                                            1. Same as Method 1. Section 3. atattons 1
                                            2, Vollaro, Robert F. Recommended
                                           Procedure for Sample Traverses in Ducts
                                           Smailay Than ig Inches.ui Diameter.-U A
                                           Environmental Protection Agency. Emission .
                                           Padu North Carolina. January 1877.
                                                               1A-8

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40 CFR Part 60,  Appendix A
Final, promulgated
                          METHOD 2A.   DIRECT MEASUREMENT OF GAS VOLUME
                                  THROUGH PIPES AND SMALL DUCTS
            1.   Applicability and Principle
                 1.1   Applicability.   This method applies to the measurement of
            gas flow rates in pipes and small ducts, either in-line or at
            exhaust positions, within the temperature range of 0 to 50°C.
                 1.2  Principle.  A gas volume meter is used to directly measure
            gas volume.  Temperature and pressure measurements are made to correct
            the volume to standard conditions.
            2.   Apparatus
                 Specifications for the apparatus are given below.  Any other
            apparatus that has been demonstrated  (subject to approval of the
            Administrator) to be capable of meeting the specifications will be
            considered acceptable.
                 2.1  Gas Volume Meter.  A positive displacement meter, turbine
            meter, or other  direct volume measuring device capable of measuring
            volume to within 2  percent.  The meter  shall be equipped with a
            temperature  gauge (£ 2 percent of  the minimum absolute temperature)
            and a pressure gauge  (±.2.5 mm Hg).   The manufacturer's recommended
            capacity of  the  meter  shall be sufficient  for the  expected maximum
            and minimum  flow rates at the sampling  conditions.  Temperature,
            pressure, corrosive characteristics,  and  pipe size are factors
            necessary to consider  in  choosing  a  suitable gas meter.
                  2.2  Barometer.   A mercury, aneroid,  or other barometer  capable
            of measuring atmospheric  pressure to within 2.5 mm Hg.   In many cases,
                                        2A-1

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the barometric reading may be obtained  from a nearby national
weather service station, in which case  the station value (which
is the absolute barometric pressure)  shall be requested, and  an
adjustment for elevation differences  between the weather station
and the sampling point shall be applied at a rate of minus 2.5 mm Hg
per 30-meter elevation increase, or vice-versa for elevation  decrease.
     2.3  Stopwatch.  Capable of measurement to within 1 second.
3.  Procedure
     3.1  Installation.  As there are numerous types of pipes and
small ducts that may be subject to volume measurement, it would  be
difficult to describe all possible installation schemes.  In  general,
flange fittings should be used for all  connections wherever possible.
Gaskets or other seal materials should be used to assure leak-tight
connections.  The volume meter should be located so as to avoid
severe vibrations and other factors that may affect the meter
calibration.
     3.2  Leak Test.  A volume meter installed at a location  under
positive pressure may be leak-checked at the meter connections by
using a liquid leak detector solution containing a surfactant.  Apply
a small amount of the solution to the connections.  If a leak exists,
bubbles will form, and the leak must be corrected.
     A volume meter installed at a location under negative pressure
is very difficult to test for leaks without blocking flow at  the
inlet of the line and watching for meter movement.  If this procedure
is not possible, visually check all connections and assure tight seals.
                                2A-2

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     3.3  Volume Measurement.
     3.3.1  For sources with continuous, steady emission flow rates,
record the initial  meter volume reading, meter texperaturefs),,meter
                                                              /
pressure, ar,d start tha stopwatch.  Throughout the test period,  record
the meter temperature(s) and pressure so that average values can be
determined.  At the end of the test, stop the timer and record the
elapsed time, the final volume reading, metsr temperature(s), and
pressure.  Record the barometric pressure at the beginning and end of
the test run.  Record the data on a tab!2 similar to Figure 2A-1.
     3.3,2  For sources with noncontiguous, non-steady emission flow
rates,  use the procedure in 3.3.1 with  the addition of the following.
Record  all the meter parameters and the start and stop times
corresponding to each  process  cyclical  or noncontinuous event.
4.   Calibration
      4.1   Volume Meter.  The  volume meter is calibrated against  a
standard reference meter prior to its  initial  use  i,i  the  field.  The
reference meter  is a  spirometer or liquid displacement meter with  a
capacity consistent with that of  the test meter.   Alternative
references may  be  used upon approval of the  Administrator.
      Set up  the  test  meter in a configuration  similar to  that used in the
field installation (i.e.,  in relation  to the flow moving  device).  Connect
the temperature and pressure gauges as they are to be used  in the  field.
 Connect the reference mater at the inlet of the flow line,  if appropriate
 for the meter,  and begin gas flow through the system to condition  the
 meters.  During this conditioning operation,, check the system for  leaks.
                              2 A-3

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Plant.
Date
  Run Number
Sample Location^
Barometric Pressure mm Hg
Operators	
Start
Finish
Meter Number
Meter Calibration Coefficient
                                  Last Date Calibrated
Time
Run/clock











Vol ume
Meter
reading^











Average
Static
pressure
nan Hg





Temperature
°C *K



1
1
I
j
!























             Figure 2A-1.  Volume f]ov/ rate measurement data.
                              2A-4

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     The calibration shall be run over at least three different
flow rates.  The calibration flow rates shall  be about 0.3,  0.5,
and 0.9 times the nr.ctar's rated maximum flew rate.
     For each calibration run, the data to be collected include:
reference meter initial and final volume readings, the test  meter
initial and final volume reading, meter average temperature  and
pressure, barometric pressure, and run time.  Repeat the runs at
each flow rate at least three times.
     Calculate the test meter calibration coefficient, Y , for each
run as follows:

                 (V_- - V  -)(t  + 273}      Pk
                                                           Eq. 2A-1
Where:
     Y   * Test volume mater calibration coefficient, dimension!ess.
                                            o
     Vr  * Reference meter volume reading, m .
     Vm  = Test meter volume reading, m  .
      m
     t   » Reference meter average temperature, °C.
     t   • Test meter average temperature, °C.
     P,   • Barometric pressure, mm Hg.
     P   « Test meter average static pressure, m Hg.
     f   » Final reading for run.
     i   » Initial reading for run.
     Compare the three Y  values at each of the flow rates tested
and determine  the maximum and minimum values.  The difference between
                             2A-5

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the maximum and minimum values at each flow rate should be no
greater than 0.030.  Extra runs may be required to complete this
requirement.  If this specification cannot be met in six
successive runs, the test meter is not suitable for use.  In addition,
the meter coefficients should be between 0.95 and 1.05.  If these
specifications are met at all the flow rates, average all  the Ym
values for an average meter calibration coefficient, T .
     The procedure above shall be performed at least once for each volume
meter.  Therefore, an abbreviated calibration check shall  be completed
after each field test.  The calibration of the volume meter shall be
checked by performing three calibration runs at a single,  intermediate
flow rate  (based on the previous field test) with the meter pressure
set at the average value encountered in the field test.  Calculate the
average value of the calibration factor.  If the calibration has
changed by more than 5 percent, recalibrate the meter over the full
range of flow as described above.  Note:  If the volume meter calibration
coefficient values obtained  before and after a test series differ by
more than  5 percent, the test series shall either be voided, or
calculations for the test series shall be performed using whichever
meter coefficient  value (i.e., before or after) gives the greater value
of pollutant emission rate.
     4.2   Temperature Gauge.  After each test series, check the
temperature gauge  at ambient temperature.  Use an ASTM mercury-ln-glass
reference  thermometer, or equivalent, as a reference.  If the gauge
being checked  agrees within  2 percent (absolute temperature) of
the reference,  the temperature data collected in the field shall be
considered valid.  Otherwise, the test data shall be considered
                               2A-6

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invalid or adjustments of the test results  shall  be made,  subject
to the approval  of the Administrator.
     4.3  Barometer.   Calibrate the barometer used against a  mercury
barometer prior to the field test.
5.  Calculations
     Carry out the calculations, retaining  at least one extra decimal
figure beyond that of the acquired data.  Round off figures after
the final calculation.
     5.1.  Nomenclature
     P. « Barometric pressure, mm Hg.
     P  » Average static pressure in volume meter, mm Hg.
     Q  • Gas flow rate, m/min, standard conditions.
     T « Average absolute meter temperature,  8K.
                                 3
     V  • Meter volume reading, m  .
     T * Meter calibration  coefficient, dimension!ess.
       m
      f » Final  reading  for  run.
      1  «  Initial  reading for run.
      s   • Standard conditions,  20°  C and 760 mm  Hg.
      e  «  Elapsed run time,  m1n.
                                2 A-7

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     5.2  Volume.
                                  -  V
     5.3  Gas Flow Rate.
                              V
                         Q  ' --                         Eq. 2A-3
6.  References
     6.1  United States Environmental  Protection Agency.  Standards
of Performance for New Stationary Sources,  Revisions  to Methods  1-8.
Title 40, part 60.  Washington,  D.C.   Federal  Register Vol.  42,
No. 160.  August 18, 1977.
     6.2  Rom, Jerome J.  Maintenance, Calibration, and Operation
of Isokinetic Source Sampling Equipment.   U.S. Environmental  Protection
Agency.  Research Triangle Park, N.C.   Publication No. APTD-0576.
March 1972.
     6.3  Wortman, Martin, R. Vollaro, and P.R. WestUn.  Dry Gas
Volume Meter Calibrations.  Source Evaluation Society Newsletter.
Vol. 2, No. 2.  May 1977.
     6.4  Westlin, P.R. and R.T. Shigehara.  Procedure for  Calibrating
and Using Dry Gas Volume Meters as Calibration Standards.   Source
Evaluation Society Newsletter.  Vol.  3, No. 1.  February  1978.
                              2A-8

-------
      Federal  Register / Vol. 48, No. 161 / Thursday,  August  18.  1983  / Rules  and Regulations
 Method 2A. Direct Measurement of Gas
 Volume Through Pipes and Small Ducts
   1. Applicability and Principle.
   1.1  Applicability. This method applies to
 the measurement of gas flow rates in pipes
 and small ducts, either in-line or at exhaust
 positions, within fhe temperature ranee of 0
 to 50'C.
   1.2  Principle. A gas volume meter is used
 to measure gas volume directly. Temperature
 and pressure measurements are made to
 correct the volume to standard conditions.
   2. Apparatus.
   Specifications for the apparatus are given
 below. Any other apparatus that has been
 demonstrated (subject to approval of Ihe
 Administrator) to be capable of meeting the
 specifications will be considered acceptable.
   2.1   Gat Volume Meter. A positive
 displacement meter, turbine meter, or other
 direct volume measuring device capable of
 measuring volume to within 2 percent The
 meter shall be equipped with a temperature
 gauge (± percent of the minimum absolute
 temperature) and a pressure gauge (±2.5 mm
 Hg). The manufacturer's recommended
 capacity of the meter shall be sufficient for
 the expected maximum and minimum flow
 rates at the sampling conditions.
Temperature, pressure, corrosive
 characteristics, and pipe size are factors
 necessary to consider in choosing a suitable
gas meter.
  12  Barometer. A mercury, aneroid, or
 other barometer capable of measuring
 atmospheric: pressure to within 2.5 mm Hg. In
 many cases, the barometric reading may be
 obtained from a nearby national weather
 service station, in which case the station
value (which is the absolute barometric
pressure) shall be requested, and an
adjustment for elevation differences between
the weather station and the sampling point
shall be applied at a rate of minus 2.5 mm Hg
per 30-meter elevation increase, or vice-versa
for elevation decrease.
 13  Stopwatch. Capable of measurement
to within 1 second.
  3. Procedure.
 3.1  Installation. As there are numerous
types of pipes and small ducts that may be
subject to volume measurement, it would be
difficult to describe all possible installation
schemes. In general, flange fittings should be
used for all connections wherever possible.
Gaskets or other seal materials should be
used to assure leak-tight connections. The
volume meter should be located so as to
avoid severe vibrations and other factors that
may affect the meter calibration.
  3J  Leak Test. A volume meter installed
at  a location under positive pressure may be
leak-checked at the meter connections by
using a liquid leak detector solution
containing • surfactant Apply a small
amount of the solution to the connections. If a
leak exists, bubbles will form, and the leak
must be corrected
  A volume meter installed at a location
under negative pressure is very difficult to
test for leaks without blocking flow at the
inlet of the line and watching for meter
movement If this procedure is not possible.
visually check all connections and assure
tight seajs.
  3.3   Volume Measurement.
  3.3.1  For sources with continuous, steady
emission flow rates, record the initial meter
volume reading, meter temperature(s), meter
pressure, and start the stopwatch.
Throughout the test period, record the meter
temperature(s) and pressure so that average
values can be determined. At the end of the
test stop the timer and record the elapsed
time, the final volume reading, meter
temperatuK(s), and pressure. Record the
barometric pressure at the beginning and end
of the test run. Record the data on a table
similar to Figure 2A-1.
MUJNQCOOC (SSO-60-M
  3.3.2  For sources with noncontinuous.
non-steady emission flow rates, use the
procedure in 3.3.1 with the addition of the
following: Record ail the meter parameters
and the start and stop times corresponding to
each process cyclical or noncontinuous event.
  4. Calibration.
  4.1  Volume Meter. The volume meter is
calibrated against a standard reference meter
prior to its initial use in the field. The
reference meter is a spirometer or liquid
displacement meter with a capacity
consistent with that of the test meter.
   Alternately, a calibrated, standard pitot
may be used as the reference meter in
conjunction with a wind-tunnel assembly.
Attach the test meter to the wind tunnel so
 that the total flow passes through the test
meter. For each calibration run. conduct a 4-
point traverse along one stack diameter  at a
 position at least eight diameters of straight
 tunnel downstream and two diameters
 upstream of any bend, inlet, or air mover.
Determine the traverse point locations as
 specified in Method 1. Calculate the reference
volume using the velocity values following
the procedure in Method 2, the wind tunnel
cross-sectional area, and the run time.
   Set up the test meter in a configuration
 similar to that used in the field installation
 (i^., in relation to the flow moving device).
 Connect the temperature and pressure gauges
 as they are to be used in the field. Connect
 the reference meter at the inlet of the flow
 line, if appropriate for the meter, and begin
 gas flow through the system to condition the
 meters. During this conditioning operation.
 check the system for leaks.
   The calibration shall be run over at least
 three different flow rates. The calibration
 flow rates shall be about 0.3, 0.6, and 0.9
 times the test meter's rated maximum flow
 rate.
   For each calibration run, the data to be
 collected include: reference meter initial and
 final volume readings, the test meter initial
 and final volume reading, meter average
 temperature and pressure, barometric
 pressure, and run time. Repeat the runs  at
 each flow rate at least three times.
  Calculate the test meter calibration
coefficient, Y,..' for each run as follows:
   Y.  =
                              (P.
Eq. 2A-1
Ym=Test volume meter calibration
    coefficient, dimensionless.
Vr=Reference meter volume reading, m3.
VM=Test meter volume reading, m1.
tr = Reference meter average temperature,
     °C.
tm=Test meter average temperature,  °C.
Pb=Barometric pressure, mm Hg.
P,=Test meter average static pressure, mm
    Hg.
f=Final reading for run.
i=Initial reading for run.
   Compare the three Ym values at each
of the flow rates tested 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
 runs may be required to complete this
 requirement. If this specification cannot
 be met in six successive runs, the test
 meter it not suitable for use. In addition.
 the metercoefficients should be
 between  0.95 and 1.05. If these
 specifications are  met at all the flow
 rates, average all the Ym values from
 runs meeting the specifications to obtain
  an average meter calibration coefficient,
 Y«.
    The procedure above shall be
  performed at least once for each volume
  meter. Thereafter, an abbreviated
  calibration check shall be completed
  following each field test. The calibration
  of the volume meter shall be checked by
  performing  three calibration runs at a
  single, intermediate flow rate (based on
  the  previous field test) with the meter
  pressure set at the average value
  encountered in the field test. Calculate
  the average value of the calibration
  factor. If the calibration has changed by
  more than 5 percent recalibrate the
  meter over the full range of flow as
  described above.
    Note.—If the volume meter calibration
  coefficient values obtained before and after a
  test series differ by more than 5 percent, the
  test series shall either be voided, or
  calculations for the test series shall be
  performed using whichever meter coefficient
  value (i.e.. before or after) gives the greater
  value of pollutant emission rate.
                                                            2A-9

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         FodenI Register / Vol. 48, No. 161 / Thursday, August 18,1983 / Rules and Regulations     3759;
Plant,
Data
  Run Nusber
Sample  Location
Baroisetric Pressure tna Hg
Operators	
Start
Finish
Meter Nicsber
Meter Calibration Coefficient
                                    Last Date Calibrated

Time
Run/clock'










j
Volume
Heter
reading











Average

Static
t oressure
mn Kg






i

•


Temperature
•C ' "-••*
*








•>
•
•
i
\














*



•

             Figure 2A-1.  Voluse flow rate eeasuresent data.
                                 2 A-10

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 Federal Register  /  Vol. 48. No. 161  / Thursday,  August 18.  1983  /  Rules  and Regulations
  4.2  Temperature Gauge. After each
 test series, check the temperature gauge
 at ambient temperature. Use an
 American Society for Testing and
 Materials (ASTM) mercury-in-gJass
 reference thermometer, or equivalent, as
 a reference. If the gauge being checked
 agrees within 2 percent ('absolute
 temperature) of the reference, the
 temperature data collected in the field
 shall be considered valid. Otherwise,
 the test data shall be considered invalid
 or adjustments of the test results shall
 be made, subject to the approval of the
 Administrator.
  43 Barometer. Calibrate the barometer
 used against a mercury barometer prior to the
 field test
  5. Calculations.
  Carry out the calculations, retaining at
 least one extra decimal figure beyond that of
 the acquired data. Round off figures after the
 final calculation.
 5.1 Nomenclature
 P»- Barometric pressure, mm Hg.
 P,=Average static pressure in volume meter,
*   mm Hg.
 Q.^Gas flow rate, m'/min, standard
     conditions.
 T»=» Average absolute meter temperature, "K.
 Vm«= Meter volume reading, ma.
 Y_=Average meter calibration coefficient
     dimensionless.
 f=Final reading for test period.
 IK Initial reading for test period.
 •.Standard conditions, 20' C and 780 mm
     Hg.
 0— Elapsed test period time, mln.
 5.2  Volume.
                             (P» + PI)
    V.  -  03863 Y. (V.TV.J
                               T.
 Eq.ZA-2

 5-J  Gas Flow Rate.
                    V.,
         Q.   - 	
                    0
 Eq. 2A-3
   8. Bibliography.
   6.1  Rom. Jerome J. Maintenance,
 Calibratioa and Operation of Isokinetic
 Source Sampling Equipment U.S.
 Environmental Protection Agency. Research
 Triangle Park. N.C. Publication No. APTD-
 0578. March 1972.
   &2  Wortman. Martin. R. Vollaro, and P.R.
 Wesdin. Dry Gas Volume Meter Calibrations.
 Source Evaluation Society Newsletter. Vol. 2.
 No. 2. May 1977.
   8J  Westlin. PJL and R.T. Shigehara.
 Procedure for Calibrating and Using Dry Gas
 Volume Meters as Calibration Standards.
 Source Evaluation Society Newsletter. Vol. 3,
 No. 1. February 197B.
                                                   2A-11

-------
40 CFR Part 60,  Appendix  A
Final,  promulgated
                   METHOD 2B -  DETERMINATION OF  EXHAUST GAS VOLUME
                     FLOW RATE  FROM GASOLINE VAPOR INCINERATORS
         Applicability and Principle
              1.1   Applicability.   This  method applies to the measurement of
         exhaust volume flow rate  from incinerators that process gasoline
         vapors  consisting primarily of  alkanes, alkenes, and/or arenes (aromatic
         hydrocarbons).  It is  assumed that the amount of auxiliary fuel  is
         negligible.
              1.2  Principle.  The incinerator exhaust flow rate is determined
         by carbon balance.  Organic carbon concentration and volume flow rate
         are measured at the incinerator inlet.  Organic carbon, carbon dioxide
         (C02)»  and carbon monoxide (CO) concentrations are measured at the
         outlet.  Then the ratio of total carbon at the  incinerator inlet and
         outlet is multiplied by the inlet volume to determine the exhaust
         volume and volume flow rate.
         2.  Apparatus
              2.1  Volume Meter.  Equipment described  in Method 2A.
              2.2  Organic Analyzers (2).  Equipment described in Method 25A or
         25B.
              2.3  CO Analyze--.  Equipment described  in  'lethod 10.
              2.4  C02 Analyzer.  A nondispersive  infrared  (NDIR) CO^ analyzer
         and supporting equipment with comparable  specificetions  as CO analyzer
         described in Method 1C.

-------
3.  Procedure
     3.1  Inlet Installation.  Install a volume meter in the vapor  line
to Incinerator inlet according to the procedure in Method 2A.   At the
volume meter inlet, install a sample probe as described in Method 25A.
Alternatively, a single opening probe may be used so that a gas sample
is collected from the centrally located 10 percent area of the vapor line
cross-section.  Connect to the probe a leak-tight, heated (1f necessary
to prevent condensation) sample line (stainless steel or equivalent) and
an organic analyzer system as described in Method 25A or 25B.
     3.2  Exhaust Installation.  Three sample analyzers are required
for the incinerator exhaust - C02, CO, and organic.  A sample manifold
with a single sample probe may be used.  Install  a sample probe as
described Method 25A or, alternatively, a single opening probe positioned
so that a gas sample 1s collected from the centrally located 10 percent
area of the stack cross-section.   Connect a leak-tight heated  sample
line to the sample probe.  Heat the sample line sufficiently to prevent
any condensation.
     3.3  Recording Requirements.  The output of each analyzer must be
permanently recorded on an analog strip chart, digital  recorder, or
other recording device.  The chart speed or number of readings per time
unit must be similar for all analyzers so that data can be correlated.
The minimum data recording requirement for each analyzer is one
measurement value per minute during the incinerator test period.
     3.4  Preparation.  Prepare and calibrate all  equipment and
analyzers according to the procedures in the respective methods.  All
calibration gases must be introduced at the connection  between the
probe and the sample line.  If a  manifold system  is used for the
                              2B-2

-------
exhaust analyzers, all  the analyzers and sample pumps must be
operating when the calibrations are done.  Note:   For the purposes
of this test, methane should not be used as an organic  calibration gas.
     3.5  Sampling.  At the beginning of the test period, record the
initial parameters for the inlet volume meter according to the
procedures in Method 2A and mark all of the recorder strip charts
to indicate the start of the test.  Continue recording  inlet organic
and exhaust CCL, CO, and organic concentrations throughout the test.
During periods of process Interruption and halting of
gas flow, stop the timer and mark the recorder strip charts  so that
data from this interruption are not included in the calculations.  At
the end of the test period, record the final parameters for the inlet
volume meter  and mark  the end  on all of  the recorder strip charts.
     3.6  Post Test Calibrations.  At the  conclusion of the sampling
period,  introduce the  calibration  gases  as specified in the respective
reference methods.   If analyzer output  does not meet the specifications
of the method,  invalidate  the  test data  for that  period.  Alternatively,
calculate the volume results using initial calibration data and using
final  calibration data and  report  both  resulting  volumes.  Then, for
emissions calculations, use the volume  measurement  resulting in the
greatest emission rate or  concentration.
4.  Calculations
      Carry  out  the calculations,  retaining at least one extra decimal
 figure beyond that of the acquired data.  Round  off figures after the
 final  calculation.
                            2B-3

-------
    4,1   Nomenclature
          CO    - Mean carbon monoxide concentration in system
           e
                 exhaust, ppmv.
          C02e  - Mean carbon dioxide concentration in system exhaust,
                 ppmv.
          HC    - Mean organic concentration in system exhaust as
                 defined by the calibration gas, ppmv.
          HCj   - Mean organic concentration in system inlet as
                 defined by the calibration gas, ppmv.
          K    - Calibration gas factor * 2 for ethane calibration gas.
                                        = 3 for propane calibration gas.
                                        = 4 for butane calibration gas.
          V    - Exhaust gas volume, m  .
           65
          V.,    - Inlet gas volume, m .
                                                o
          Q    - Exhaust gas volume flow rate, m /min.
                                              3
          Q^s   - Inlet gas volume flow rate, m /min.
          e    -.Sample run time, min.
          s    - Standard Conditions: 20°C, 760 mm Hg.
          300   - Estimated concentration of ambient C02, ppmv.
                 (COp concentration in the ambient air may be measured
                 during the test period using an NDIR and the mean
                 value substituted into the equation.)
     4.2  Concentrations.  Determine mean concentrations of inlet
organics, outlet  COp, CO, and outlet organics according to the procedures
1n the respective methods and the analyzers' calibration curves, and
for the time intervals specified  in the  applicable regulations.
                              2B-4

-------
Concentrations should be determined  on  a  parts  per million by volume
(ppmv) basis.
     4.3  Exhaust Gas Volume.   Calculate  the exhaust gas  volume as
follows:
                                  3fi -  300
     4.4  Exhaust Gas Volume Flow Rate.   Calculate the exhaust
gas volume flow rate as follows:
          Qes  =  --                                        Eq.  2B-2
5.  References
     5.1  Measurement of Volatile Organic Compounds.   U.S.  Environmental
Protection Agency.  Office of Air Quality Planning and Standards.
Research Triangle Park, N.C. 27711.  Publication No.  EPA-450/2-78-041.
October 1978.  p. 55.
     5.2  Method 10 - Determination of Carbon Monoxide
Emissions from Stationary Sources.  U.S. Environmental Protection
Agency.  Code of Federal Regulations.  Title 40, Chapter 1, part 60,
Appendix A.  Washington, D.C. Office of the Federal Register.
March 8, 1974.
                             2B-5

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     5.3  Method 2A - Determination of Gas Flow Rate
in Pipes and Small Ducts.  Tentative Method.  U.S.  Environmental
Protection Agency.  Office of Air Quality Planning  and Standards.
Research Triangle Park, M.C.  27711.  March 1980.
     5.4  Method 25A - Determination of Total  Gaseous
Organic Compounds Using a Flame lonization Analyzer.  Tentative
Method.  U.S. Environmental Protection Agency.  Office of Air
Quality Planning and Standards.  Research Triangle  Park,  N.C. 27711.
March 1980.
     5.5  Method 25B - Determination of Total  Gaseous
Organic Compounds Using a  Nondispersive Infrared Analyzer.
Tentative Method.  U.S. Environmental Protection Agency.   Office  of
Air Quality Planning and Standards.  Research Triangle Park,  N.C.  27711
March 1980.
                              2B-6

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             Federal Register /  Vol. 48, No. 161 / Thursday. August 18.1983  / Rules and Regulations
Method 2B—Determination of Exhaust Gas
Volume Flow Rate From Gasoline Vapor
Incinerators
Applicability and Principle
  1.1  Applicability. This method applies to
the measurement of exhaust volume flow rate
from incinerators that process gasoline
vapors consisting primarily of alkanes,
alkenes. and/or arenes (aromatic
hydrocarbons). It is assumed that the amount
of auxiliary fuel is negligible.
  13 Principle. The incinerator exhaust
flow rate is determined by carbon balance.
Organic carbon concentration and volume
flow rate are measured at the incinerator
inlet. Organic carbon, carbon dioxide (CDs),
and carbon monoxide (CO) concentrations
are measured at the outlet Then the ratio of
total carbon at the incinerator inlet  and outlet
is multiplied by,the inlet volume to determine
the exhaust volume and volume flow rate.
  2. Apparatus.
  2.1  Volume Meter. Equipment described
in Method 2A.
  i2  Organic Analyzer (2). Equipment
described in Method 2SA or 25B.
  2.3  CO Analyzer. Equipment described in
MethodlO.
  2.4  COt Analyzer. A nondispersive
infrared (ND1R) CO* analyzer and supporting
equipment with comparable specifications as
CO analyzer described in Method 10.
  3. Procedure.
  3.J  Inlet Installation. Install a volume
meter in the vapor line to incinerator inlet
according to the procedure in Method 2A. At
the volume meter inlet install a sample probe
as described in Method 2SA. Connect to the
probe a leak-tight heated (if necessary to
prevent condensation) sample line (Stainless
steel or equivalent) and an organic analyzer
system as described in Method 25A or 25B.
  33  Exhaust Installation. Three sample
analyzers are required for the incinerator
exhaust CO*. CO, and organic analyzers. A
sample manifold with a single sample probe
may be used. Install a sample probe as
described Method 25A. Connect a leak-tight
heated sample line to the sample probe. Heat
the sample line sufficiently to prevent any
condensation.
  3.3  Recording Requirements. The output
of each analyzer must be permanently
recorded on an analog strip chart digital
recorder, or other recording device. The chart
speed or number of readings per time unit
must be similar for all analyzers so that data
can be correlated. The minimum da4a
recording requirement for each analyzer is
one measurement value per minute.
  3.4   Preparation. Prepare and calibrate all
equipment and analyzers according to the
procedures in the respective -methods. For the
COj analyzer, follow the procedures
described in Method 10 for CO analysis
substituting COi  calibration gas where the
method calls for CO calibration gas. The span
value for the COi analyzer shall be IS percent
by volume. All calibration gases must be
introduced at the connection between the
probe and the sample line.  If a manifold
system is used for the exhaust analyzers, all
the analyzers and sample pumps must be
operating when the calibrations are done.
Note: For the purposes of this test, methane
should not be used as an organic calibration
gas.
  3.5  Sampling. At the beginning of the test
period, record the initial parameters for the
inlet volume meter according to the
procedures in Method 2A and mark all of the
recorder strip charts to  indicate the start of
the test. Continue recording inlet organic and
exhaust CO*. CO. and organic concentrations
throughout the test During periods of process
interruption and halting of gas flow, stop the
timer and mark the recorder strip charts so
that data from this interruption are not
included in the calculations. At the end of the
test period record the final parameters for
the inlet volume meter  and mark the end on
 all of the recorder strip charts.
   3.0  Post Test Calibrations. At the
 conclusion of the sampling period, introduce
 the calibration gases as specified in the
 respective reference methods. If an analyzer
 output does not meet the specifications of  the
 method, invalidate the test data for the
 period Alternatively, calculate the volume
 results using initial calibration data and using
 final calibration data and report both
 resulting volumes. Then, for emissions
 calculations, use the volume measurement
 resulting in the greatest emission rate or
 concentration.
   4. Calculations.
   Cany out the calculations, retaining at
 least one extra decimal figure beyond that of
 the acquired data. Round  off figures after the
 final calculation.
4.1 Nomenclature
CO,=Mean carbon monoxide concentration
     in system exhaust ppmv.
CO**=Mean carbon dioxide concentration in
     system exhaust ppmv.
HC,=Mean organic concentration in system
     exhaust as defined by the calibration
     gas. ppmv.
 HCi = Mean organic concentration in system
     inlet  as defined by the calibration gas.
     ppmv.
 K-Calibration  gas factor"2 for ethane
     calibration gas.
   «3 for propane calibration gas.
   -4 for butane calibration gas.
   =Appropriate response factor for other
     calibration gas.
 VM=< Exhaust gas volume, Ms.
 V,.- Inlet gas volume, M*.
 0^.=Exhaust gas volume flow rate,
 Oj.=Inlet gas volume  flow rate, m'/min.
 e=Sample run  time, min.
 s=Standard Conditions: 20° C, 780 mm Hg.
 3(10=Estimated concentration of ambient

              2B-7
    COj. ppmv. (COj concentration in the
    ambient air may be measured during the
    test period using an NDIR and the mean
    value substituted into the equation.)
  4.2  Concentrations. Determine mean
concentration of inlet organics, outlet CO>,
outlet CO, and outlet organics according to
the procedures in the respective methods and
the analyzers' calibration curves, and for the
time intervals specified in the applicable
regulations. Concentrations should be
determined on a parts per million by volume
(ppmv) basis.
  4.3  Exhaust Gas Volume. Calculate the
exhaust gas volume as follows:  •
                       K(HC.)
                 K(HC.) + COz/300

Eq. 2B-1
  4.4  Exhaust Gas Volume Flow Rate.
Calculate the exhaust gas volume flow rate
as follows:

                0-

Eq. ZB-2
  5. Bibliography.
  5.1  Measurement of Volatile Organic
Compounds. U.S. Environmental Protection
Agency. Office of Air Quality Planning and
Standards. Research Triangle Park, N.C.
27711. Publication No. EPA-450/2-78-041.
October 1978. p. 55.

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     METHOD 2C - DETERMINATION OF STACK GAS VELOCITY AND VOLUMETRIC FLOW RATE
             FROM SMALL STACKS OR DUCTS {STANDARD PITOT TUBE)
1.  Applicability and Principle
     1.1  Applicability.  The applicability of this method is identical  to
Method 2, except it is limited to stationary source stacks or ducts.less than
about 0.30 meter (12 in.) in diameter, or 0.071 m2 (113 in.2) in cross-sectional
area, but equal to or greater than about 0.10 meter (4 in.) 1n diameter, or
        2           2
0.0081 m  (12.57 in. ) in cross-sectional area.
     The apparatus, procedure, calibration, calculations, and bibliography are
the same as in Method 2, Sections 2, 3, 4, 5, and 6, except as noted in the
following sections.
     1.2  Principle.  The average gas velocity in a stack or duct is determined
from the gas density and from measurement of velocity heads with a standard
pitot tube.
2.  Apparatus
     2.1  Standard Pi tot Tube  (instead of Type S).  A standard pi tot tube
which meets the specifications of Section 2.7 of Method 2.  Use a coefficient
of 0.99 unless it is calibrated against another standard pitot tube with an
NBS-traceable coefficient.
     2.2  Alternative Pitot Tube.  A modified hemispherical-nosed pitot tube
(See Figure 2C-1), which features a shortened stem and enlarged impact and
static  pressure holes.  Use a  coefficient of 0.99 unless it  is calibrated as
mentioned in  Section 2.1 above.  This pitot tube is useful  in particulate
liquid  droplet laden gas streams when a  "back purge" is ineffective.
3.  Procedure
      Follow the general  procedures  in Section  3 of Method 2, except conduct
                                    2C-1

-------
                            FIGURE 2C-1.


          MODIFIED HEMISPHERICAL-NOSED PITOT TUBE
r>
i

ro
                                     4 STATIC HOLES 3/8 D
                                     IMPACT OPENING 1/2 D

-------
the measurements at the traverse points specified in Method 1A.  The-static
and impact pressure holes of standard pitot tubes are susceptible to plugging
in particulate-laden gas streams.  Therefore, the tester must furnish adequate
proof that the openings of the pitot tube have not plugged during the traverse
period; this can be done by taking the velocity head Up) reading at the
             i
final traverse point, cleaning out the impact and static holes of the standard
pitot tube by "back-purging" with pressurized air, and then taking  another
Ap reading.  If the Ap readings made before and after the air  purge are
the same (- 5 percent) the traverse is acceptable.  Otherwise, reject the
run.  Note that if the Ap at the final traverse point is unsuitably low,
another point may be selected.   If "back-purging" at regular  intervals is
part of the procedure, then take comparative Ap readings, as  above, for  the
last two back purges at which  suitably high Ap readings  are observed.
                                     2C-3

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48956
Federal Register / Vol. 48. No. 205 / Friday,  October 21. 1983 f Proposed Rules
                                                             lees thsa about O30 meter (12 to.) in diameter.
                                                             or 0m ms(tl3 to,*, in cross Mctional ana.
                                                             bat aqnal to or prMtar than aboot 0.10 mttw
                                                             (4 in.) in diametar or OOOW m* (1ZJ5T in.1) in
                                                             croM-Mctiooal ana.
                                                               Tha apparatus, pncadun, calibratton.
                                                             catoolatfaBi. and bibliography an tfaa MIM
                                                             aa in Method 2. Sactiaoa 2.3,4. Vand 8.
                                                             axcapt aanotad in OM following aKtfooa.
                                                               12 Prindpk. Tie average gaa Takxaty in a
                                                             •tack or dfect ia detmninad from tha gas
                                                             dnsitir and fton meaaannent at velocity
                                                             head* with a standard pilot tab*.
                      1 lUfanmca Method 2C U added to
                   Appendix A as follows:
                    MuthuttX-D*
                          i of Stack Go*
                    Velocity oadVohtptetiic Flow Rot* FT**
                   Smell Stockier Duct* (Standard Pitt* TubeJ
                     14 ApptobiHty. Its applicability of tbia
                   BM&ri is identical to Method 2. except it is
                   (Mad to stationary source stacks or docti
  11 Standard Pftot Tube (instead ofType
8). A standard pilot tube whidrmeels the
specifications of Section^ of Method 2. Use
acoefflnsirt of OOB anhss It la calibrated
agatost another standard pilot tabs with an
NBS-tneaabk coefficient
  12 AfieraathrePHot Tube. A modified
bemispherlcal-ooeed pilot tube (see Figure
2C-1). which laatarea a shortened stem and
enlarged Impact and static pressure holes.
Use a coefficient of O» unless it U calibrated
as nentianed in Section U above. This pitot
tabs is oaafol tat particubue- Uqnid droplet
laden gas streams when a "back purge'* is
                                                            2C-4

-------
                Federal Register  / Vol. 48, No. 205 / Friday,  October  21,  1983  / Proposed  Rules
48957
                                                                                      Mt
                                                                                                                  tit
                                                                                                            o
                                                                                                                  • •
                                                                                                              U_
                       Figure 2C-1.  Modified healspherical-nosed p1tot.tube.
  Follow the general procedure* la Section 3
of Method 2, except conduct the
measurements «t thetnverM point* specified
in Method 1A. The static and impact pressun
boles of standard pitot tubes an susceptible
to plugging in particulate-laden gas stream*.
Therefore, the tester must famish adequate
proof that the openings of the pitot tnbe have
not plugged during the traverse period; this
can be done by taking the velocity head (Ap)
heading at the final traverse point, cleaning
out the impact and statk holes of the
standard pitot tube by "back-purging" with
pressurized air, and then taking another Ap
reading. If the A readings made before and
after the air purge an the same (±5 percent)
the traverse is acceptable. Otherwise, reject
the run. Note that if the AP at the final
traverse point is unsuitably low. another
point may be selected. If "back purging" at
regular intervals is part of the procedure, then
•take comparative Ap readings, as above, for
the last two back purges at which suitably
high Ap readings are observed.
                                                         2C-5

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             METHOD 18.  MEASUREMENT OF GASEOUS ORGANIC
              COMPOUND EMISSIONS BY GAS CHROMATOGRAPHY
                              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 potentially explosive atmospheres.]
1.  Applicability and Principle
     1.1  Applicability.  This method applies to 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) can polymerize before analysis, or (3) have
very low vapor pressures at stack or instrument conditions.
     1.2  Principle.   This method is based on separating the major
components of a gas mixture with a gas chromatograph (GC) and measuring
the separated components with a suitable detector.
     The retention times of each separated component are compared with
those of known compounds under identical conditions.  Therefore, the
analyst confirms the identity and approximate concentrations of the
organic emission components beforehand.  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 detector saturation, gas stream filtration to eliminate participate
matter, and prevention of moisture condensation.
                                  18-1

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2.  Range and Sensitivity
     2.1  Range.  The range of this nethod is from about 1 part per
Million (ppm) to the upper limit governed by GC detector saturation or
col tan 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 detectable concentration of that compound, or the
concentration that produces a signal-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 chromatography techniques typically provide a precision of 5 to
10 percent relative standard deviation (RSD), but an experienced GC
operator with a reliable instrument can readily achieve 5 percent RSO.
For this 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 preparation 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 temperature
programming.
     The analytical system is demonstrated to be essentially free from
contaminants by periodically analyzing blanks that consist of hydrocarbon-
free air or nitrogen.
                                 18-2

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     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 eliminate errors in concentration calculations
due to the volume of water vapor in the samples, moisture concentrations
are determined for each sample, and a correction factor is applied to
any sample with greater than 2 percent water vapor.
5.   Presurvey and Presurvey Sampling
     A presurvey shall be performed on each source to be tested.  The
purpose of the presurvey is to obtain all information necessary to
design the emission test.  The most important presurvey data are the
average stack temperature and temperature range, approximate particulate
concentration, static pressure, water vapor content, and identity and
expected concentration of each organic compound to be analyzed.  Some of
this information can be obtained from literature surveys, direct knowledge,
or plant personnel.  However, presurvey samples of the gas shall be
obtained for analysis to confirm the identity and approximate concentrations
of the specific compounds prior to the final testing.
     5.1  Apparatus.
     5.1.1  Teflon Tubing.  (Mention of trade names or specific products
does not constitute endorsement by the U.S. Environmental Protection
Agency.)  Diameter and length determined by connection requirements of
cylinder regulators and the GC.  Additional tubing is necessary to
connect the GC sample loop to the sample.
                                18-3

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     5.1.2  Gas Chromatograph.  GC with suitable detector, columns,
temperature-controlled sample loop and valve assembly, and temperature
programable oven, if necessary.  The GC shall achieve sensitivity
requirements for the compounds under study.
     5.1.3  Pump.  Capable of pumping 100 ml/min.  For flushing sample
loop.
     5.1.4  Flow Meter.  To accurately monitor sample loop flow rate of
100 ml/min.
     5.1.5  Regulators.  Used on gas 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.  1.0- and 10-microliter size, calibrated, maximum
accuracy (gas tight) for preparing standards and for injecting head
space vapor from liquid standards in retention time studies.
     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, amber-colored glass jars
with Teflon-lined lids for compensate sample collection.   Size depends
on volume of compensate.
     5.1.11  Soap Film Flowmeter.  To determine flow rates.
                      t
     5.1.12  Tedlar Bags.  10- and 50-liter capacity, for preparation of
standards.
     5.1.13  Dry Gas Meter with Temperature and Pressure Gauges.   Accurate
to +2 percent, for preparation of gas standards.
     5.1.14  Midget Impinger/Hot Plate Assembly.   For preparation of gas
standards.
                                 18-4

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     5.1.15  Sample Flasks.  For presurvey samples, must have gas-tight
seals.
     5.1.16  Adsorption Tubes.   If necessary, blank tubes filled with
necessary adsorbent (charcoal,  Tenax, XAD-2, etc.) for presurvey samples.
     5.1.17  Personnel Sampling Pimp.  Calibrated, for collecting adsorbent
tube presurvey samples.
     5.1.18  Dilution System.  Calibrated, the dilution system is to be
constructed following the specifications of an acceptable method.
     5.2  Reagents.
     5.2.1  Deionized Distilled Water.
     5.2.2  Chloroform.
     5.2.3  Calibration Gases.   A series of standards prepared for every
compound of Interest.
     5.2.4  Calibration Solutions.  Samples of all the compounds of
interest in a liquid form, for retention time studies.
     5.2.5  Extraction Solvents.  For extraction of adsorbent tube
samples In preparation for analysis.
     5.2.6  Fuel.  As recommended by the manufacturer for operation of
the GC.
     5.2.7  Carrier Gas.   Hydrocarbon free, as recommended by the
manufacturer for operation 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.
     5.3.1  Collection of Samples with Glass Sampling Flasks.  Presurvey
samples can be collected in precleaned 250-ml double-ended glass sampling
                                18-5

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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 stopcocks,
barrels, and receivers with chloroform.  Clean all glass ports with a
soap solution, then Hnse with tap and deionized distilled water.  Place
the flask In a cool glass annealing furnace and apply heat up to 550°C.
Maintain at this temperature for 1 hour.  After this time period, shut
off and open the furnace to allow the flask to cool.  Grease the stopcocks
with stopcock grease and return them to the flask receivers.  Purge the
assembly with high-purity nitrogen for 2 to 5 minutes.  Close off the
stopcocks after purging to maintain a slight positive nitrogen pressure.
Secure the stopcocks with tape.
     Presurvey samples can be obtained either by drawing the gases Into
the previously evacuated flask or by drawing the gases Into and purging
the flask with a rubber suction 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 (00) glass
tee to the flask Inlet with a short piece of Teflon tubing.  Select a
6-mm 00 boroslllcate sampling probe, enlarged at one end to a 12-nm 00
and of sufficient length to reach the centrold of the duct to be sampled.
Insert a glass wool plug 1n the enlarged end of the probe to remove
partial late natter.  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, and purge the probe with the rubber suction bulb.  After
the probe 1s completely purged  and filled with duct gases, open the
                                 18-6

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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 stopcocks 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 00 glass
probe as described in Section 5.3.1.1.  Place the filter end of the
probe at the centroid of the duct, and apply suction with the bulb to
completely purge the probe and flask.  After the flask has been purged,
close off the stopcock near the suction 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 aluminized Mylar bags can
also be used to obtain the presurvey sample.  Use new bags, and leak
check them before field use.  In addition, check the bag before use for
contamination by filling it with nitrogen or air, and analyzing the gas
by GC at high sensitivity.   Experience Indicates that it is desirable to
allow the inert gas to remain in the bag about 24 hours or longer to
check for desorption of organics from the bag.  Follow the leak check
and sample collection procedures given in Section 7.1.
     5.3.3  Determination of Moisture Content.  For combustion or water-
controlled processes, obtain the moisture content from plant personnel
or by measurement during the presurvey.  If the source is below 50°C,
measure the wet bulb and dry bulb temperatures, and calculate the moisture
content using a psychrometric chart.  At higher temperatures, use Method 4
to determine the moisture content.
                                18-7

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     5.4  Detenrination of Static Pressure.  Obtain the static pressure
fro* the plant personnel or Measurement.  If a type S pitot tube and an
Inclined manometer are used, take care to align the pi tot tube 90° from
the direction of the flow.  Disconnect one of the tubes to the nanometer,
and read the static pressure; note whether the reading 1s positive or
negative.
     5.5  Collection of Presurvey Samples with Adsorption Tube.  Follow
Section 7.4 for presurvey sampling.
6.  Analysis Development
     Presurvey samples shall be used to develop and confirm the best
sampling and analysis scheme.
     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 resolution and rapid analysis time.
The choice of an appropriate column can be aided by a literature search,
contact with manufacturers of GC columns, and discussion with personnel
at the emission source.
     Most column manufacturers keep excellent records on their products.
Their technical service departments may be able to recommend appropriate
columns and detector type for separating the anticipated compounds, and
they may be able to provide Information on Interferences, optimum operating
conditions, and column limitations.
     Plants with analytical laboratories nay be able to provide information
on their analytical procedures, Including extractions, detector type,
column types, compounds emitted, and approximate concentrations.
                                 18-8

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     6.1.2  Preliminary GC Adjustment.  Using the standards and column
obtained in Section 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 adsorbent, extract the sample as recommended by the
manufacturer for removal of the compounds with a' solvent suitable to the
type of GC 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/1nfrared techniques.  A GC/MS system
is recommended.
     Use the GC conditions determined by the procedure of Section 6.1.2
for the first injection.  Vary the GC parameters during subsequent
injections to determine the optimum settings.  Once the optimum settings
have been determined, perform repeat  injections of the sample to determine
the retention time of each compound.  To  Inject a sample, draw sample
through the loop at a constant rate (100 ml/min for 30 seconds).  Be
careful not to  pressurize the gas in  the  loop.  Activate the sample
valve, and record injection time, loop temperature, column temperature,
carrier flow rate, chart  speed, and attenuator setting.  Calculate the
retention time  of each peak using the distance from injection to the
peak maximum divided by the chart speed.  Retention times should be
repeatable within 0.5 seconds.
                                 18-9

-------
     If th« concentrations are too high for appropriate detector response,
a SMller sample loop or dilutions nay be used for gas samples, and, for
liquid samples, dilution with solvent 1s appropriate.  Use the standard
curves (Section 6.3) to obtain an estimate of the concentrations.
     Identify all peaks by comparing the known retention times of compounds
expected to be 1n the sample to the retention tines of peaks in the
sample.  Identify any remaining unidentified 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.  If the presurvey samples are collected
1n an adsorbent tub* (charcoal, XAD-2, Tenax, etc.), prepare the standards
1n the same solvent used for the extraction procedure for the adsorbent.
Prepare several standards for each compound throughout the range of the
sample.
     6.2.1  Cylinder Calibration Gases.  If available, use NBS reference
gases or commercial gas mixtures certified through direct analysis for
the calibration curves.
     6.2.1.1  Optional Cylinder Approach.  As an alternative procedure,
maintain high and low calibration standards.  Use the high concentration
(50 to 100 pom) standard to prepare a three-point calibration curve with
an appropriate dilution technique.  Then use the low-concentration
standard to verify the dilution technique.  Use this same approach also
to verify the dilution techniques for high-concentration source gases.
     To prepare the diluted calibration samples, use calibrated rotameters
to meter both the high concentration calibration gas and the diluent
gas.  Adjust the flow rates through the rotaneters with micrometer
                                 18-10

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valves to obtain the desired dilutions.  A positive displacement pump or
other metering techniques may be used in place of the rotameter to
provide a fixed flow of high concentration gas.
     To calibrate the rotameters, connect each rotameter between the
diluent gas supply and a suitably sized bubble meter, spirometer, or wet
test meter.  While it is desirable to calibrate the calibration gas
flowmeter with calibration gas, generally the available amount of this
gas will preclude it.  The error introduced by using the diluent gas is
insignificant for gas mixtures of up to 1,000 to 2,000 ppm of each
organic component.  Record the temperature and atmospheric pressures as
follows:

                        Q2 » Qi     p2^                        Eo.- 18-1
Where:
       Q2 =    Flow rate at new absolute temperature (T2) and new absolute
               pressure (P2).
       Qj =    Flow rate at calibration absolute temperature (Tx) and
               absolute pressure (Pi).
Connect the rotameters to the calibration and diluent gas supplies using
6-mm Teflon tubing.  Connect the outlet side of the rotameters through a
connector to a leak-free Tedlar bag as shown in Figure 18-5.  (See
Section 7.1 for leak check procedures.)  Adjust the gas flows to provide
the desired dilution, and fill the bag with sufficient gas for calibration.
Be careful not to fill to the point where it applies additional pressure
on the gas.  Record the flow rates of both rotameters, the ambient
temperature, and atmospheric pressure.  Calculate the concentration of
diluted gas as follows:
                                   106(X q )
                              r*  —      a a                     r_  io_o
                                 13-11

-------
Where:
          C  = Concentration of component "a"  in ppra.
          X  = Hole fraction of component "a"  in the calibration gas to
           a   be diluted.
          q  = Flow rate of component "a" at measured temperature and
               pressure.
          qd = Diluent gas flow at measured temperature and pressure.
Use single-stage dilutions to prepare calibration mixtures up to about
1:20 dilution factor.  For greater dilutions,  use a double dilution
system.  Assemble the apparatus, as shown in Figure 18-6, using calibrated
flowmeters of suitable range.  Adjust the control valves so that about
90 percent of the diluted gas from the first stage is exhausted, and
10 percent goes to the second stage flowmeter.  Fill the Tedlar bag with
the dilute gas from the second stage.  Record  the temperature, ambient
pressure, and water manometer pressure readings.  Correct the flow
reading in the first stage as indicated by the water manometer reading.
Calculate the concentration of the component in the final gas mixture as
follows:

                         c. -10" x   /   **\ /  <*\   £q  18.3
Where:
          Ca = Concentration of component "a" in ppm.
          X  = Hole fraction of component "a" in original gas.
         qal = Flow rate of component "a" in stage 1.
         q.2 s Flow rate of component "a" in stage 2.
          a
         qdl = Flow rate of diluent gas in stage 1.
         q .2 = Flow rate of diluent gas in stage 2.
     Further details of the calibration methods for rotaraeters  and the
dilution system can be found in Citation 21 in Section 8.
                                 18-12

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     6.2.2  Preparation of Standards from Volatile Materials.  Record
all data shown on Figure 18-3.
     6.2.2.1  Bag Technique.   Evacuate a 10-liter Tedlar bag that has
passed a leak check (see Section 7.1), and meter in 5.0 liters of nitrogen
through a 0.5 liter per revolution dry test meter.  While the bag is
filling, use a 0.5-ml syringe to inject a known quantity of the material
of interest through the wall  of the bag or through a septum-capped tee
at the bag inlet.  Withdraw the syringe needle, and immediately cover
the resulting hole with a piece of masking tape.  In a like manner,
prepare dilutions having other concentrations.  Prepare a minimum of
three concentrations.  Place each bag on a smooth surface, and alternately
depress opposite sides of the bag 50 times to mix the gases.  Record the
average meter temperature, gas volume, liquid volume, barometric pressure,
and meter pressure.
     Set the electrometer attenuator to the XI  position.  Flush the
sampling loop with zero helium or nitrogen, and activate the sample
valve.  Record the Injection time, sample loop  temperature, column
temperature, carrier gas flow rate, chart speed, and attenuator setting.
Record peaks and detector responses that occur  in the absence of any
sample.  Maintain conditions.  Flush the sample loop for 30 seconds at
the rate of 100 ml/min with one of the calibration mixtures, and open
the sample valve.  Record the injection time.   Select the peak that
corresponds to the compound of interest.  Measure the distance on the
chart from the injection time to the time at which the peak maximum
occurs.  Divide this quantity by the chart speed, and record the resulting
value as the retention time.
                                 18-13

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     6.2.2.2  Preparation of Standards from Less Volatile Liquid Materials.
Use the equipment shown in Figure 18-8.  Calibrate the dry gas meter
with a wet test meter or a spirometer.  Use a water nanometer for the
pressure gauge and glass, Teflon, brass, or stainless steel for all
connections.  Connect a valve to the Inlet of the 50-liter 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 water to reach boiling.
Connect the bag to the Implnger outlet.  Record the Initial meter reading,
open the bag Inlet valve, and open the cylinder.  Adjust the rate so
that the bag will be completely filled In approximately 15 minutes.
Record meter pressure, temperature, and local barometric pressure.
     Fill the syringe to the desired liquid volume with the material to
be evaluated.  Place the syringe needle Into the Implnger Inlet using
the septum provided, and Inject the Ifquid Into the flowing 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.
     Complete filling of the bag; note and record the meter pressure and
temperature at regular Intervals, preferably 1 minute.
     When the bag Is filled, stop the pump, and close the bag Inlet
valve.  Record the final meter reading.
     Disconnect the bag from the Implnger outlet, and set it aside for
at least 1 hour to equilibrate.   Analyze the sample within the proven
life period of its preparation.
                                 18-14

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     6.2.2.3  Concentration Calculations.  Average the meter temperature
(T ) and pressure (PJ readings over the bag filling process.
  IB                 HI
     Measure the solvent liquid density at room temperature by accurately
weighing a known volume of the material on an analytical balance to the
nearest 1.0 milligram.  Take care during the weighing to minimize
evaporation of the material.  A ground-glass stoppered 25-ml volumetric
flask or a glass- stoppered specific gravity bottle is suitable for
weighing.  Calculate the result 1n terns of g/ml.  As an alternative,
literature values of the density of the liquid at 20°C may be used.
     Calculate the concentration of material in the sample in mg/ liter
at standard conditions as follows:
                    r        = 760 (L ) (p) (293 + T)
                     std so1                        "
Where:
    ^std sol = Standard solvent concentration, mg/std liter.
          Ly = Liquid volume Injected, ml.
           p = Liquid density at room temperature, g/ml.
          TB = Meter temperature, °C.
      Mf' MJ = Final and initial meter reading, liters.
        Pbar = Local barometric pressure (absolute), mi Hg.
          P|R = Meter pressure (gauge), mm Hg.
     6.3  Preparation of Calibration Curves.   Obtain gas standards as
described in Section 6.2 such that three concentrations per attentuator
range are available.  Establish proper GC conditioning, then flush the
sampling loop for 30 seconds at a rate of 100 ml/min.  Allow the sample
loop pressure to equilibrate with atmospheric pressure, and activate the
injection valve.  Record the standard concentration, attentuator setting,
                                 18-15

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Injection tine, chart speed, retention time, peak area, sample loop
temperature, col inn teaperature, and carrier gas flow rate.  Repeat the
standard Injection until two consecutive Injections give area counts
within 5 percent of their average.  The average Multiplied by the attenuator!
setting 1s then the calibration area value for that concentration.
     Repeat this procedure for each standard.  Plot concentrations along
the abscissa and the calibration area values along the ordlnate.  Perform
a regression analysis, and draw the least squares line.
     6.4  Optional Use of Prepared Cylinders for Dilution Calibration
Checks, and Response Factor Determinations.  A set of three standards of
the major component in the emissions is required.  This set of standards
can be taken into the field and thereby replace the need to prepare
standards as described in Section 6.2.2.
     The high concentration standard can be run through the dilution
system to assess the accuracy of the system.  First, prepare a calibration
curve using the three standards following the procedure described in
Section 6.3.  Then, prepare a dilute sample using the high concentration
standard so that the dilute sample will fall within the lower limits of
the calibration curve.
     Next, analyze the dilute sample, and calculate the measured
concentration from the calibration curve as described in Section 6.3.
The dilute concentration calculated from the analysis shall be within
10 percent of the concentration expected from the dilution system;
otherwise determine the source of error in the dilution system, and
correct it.
     The calibration curve from the cylinder standards for a single
organic can also be related to the GC response curves of all the compounds
                                 18-16

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In the source by response factors developed in the laboratory.  In the
field, the single calibration curve from the cylinder standards and the
calculated response factors measured in the laboratory can then be used
to replace the need to prepare and analyze calibration standards for
each organic compound (see Section 6.5 on daily quality control procedure).
     Recheck the relative peak area of one of the calibration standards
dally to guard against degradation.  If the relative peak areas on
successive days differ by more than 5 percent, remake all of the standards
before proceeding to the final sample analyses.
     6.5  Evaluation of Calibration and Analysis Procedure.  Immediately
after the preparation of the calibration curve and prior to the final
sample analyses, perform the analysis audit described in Part 61,
Appendix C, Procedure 2:  "Procedure for Field Auditing GC Analysis"
(47 FR'39179, September 7, 1982).  The Information required to document
the analysis of the audit samples  has been included on the example data
sheets shown in Figures 18-3 and 18-7.  The audit analyses shall agree
with the audit concentrations within 10 percent.  When available, the
tester may obtain audit cylinders  by contacting:  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:
(a) the gas manufacturer certifies the audit cylinder as described in
Section 5.2.3.1 of Method 23 and (b) the gas manufacturer obtains an
independent analysis of the audit  cylinders to verify this analysis.
Independent analysis 1s 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
                                 18-17

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those used for the gas Manufacturer's analysis.  Verification is complete
and acceptable when the independent analysis concentration is within
5 percent of the gas manufacturer's concentration.
7.  Final Sampling and Analysis Procedure
     Considering safety (flame hazards) and the source conditions,
select an appropriate sampling and analysis procedure (Section 7.1, 7.2,
7.2, or 7.4).  In situations where a hydrogen flame 1s a hazard and no
Intrinsically safe GC 1s suitable, use the flexible bag collection
technique or an adsorption technique.  If 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 gases 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 storage
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 Analysis
     7.1.1  Evacuated Container Sampling Procedure.  In this procedure,
the bags are filled by evacuating the rigid air-tight container holding
the bags.  Therefore, check both the bags and the container for leaks
before and after use as follows:  Connect a water manometer using a tee
connector between the bag or rigid container and a pressure source.
Pressurize the bag or container to 5 to 10 cm H20 (2 to 4 in. H20), and
allow it to stand overnight.  A deflated bag indicates a leak.
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      7.1.1.1  Apparatus.
      7.1.1.1.1  Probe.   Stainless steel, Pyrex glass, or Teflon tubing
 probe, according to the duct temperature, with 6.4-mm 00 Teflon tubing
 of sufficient length to connect 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 gas flow.
      7.1.1.1.4  Pump.   Leakless Teflon-coated diaphragm-type pump or
 equivalent.   To  deliver at least 1 liter/min.
      7.1.1.1.5  Charcoal  Adsorption Tube.  Tube filled with activated
 charcoal,  with glass wool  plugs at each end, to adsorb organic vapors.
      7.1.1.1.6  Flowmeter.   0  to 500-ml flow range; with manufacturer's
 calibration  curve.
      7.1.1.2  Sampling  Procedure.   To obtain a sample, assemble the
 sample train as  shown in  Figure 18*9.   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 centroid
 of the stack,  and start the pump with the needle valve adjusted 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 evacuate
 until the rotameter indicates  no flow.  Then position the sample and
 vacuum lines for sampling, and begin the actual sampling, keeping the
 rate proportional to the stack velocity.  As a precaution, 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
                                  18-19

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the source temperature, baroaetric pressure, ambient temperature, sampling
flow rate, and initial and final sampling tine on the data sheet shown
in Figure 18-10.   Protect the Tedlar bag and its container from sunlight.
When possible, perfom 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.  Use a pump and
needle valve constructed of stainless steel or some other material not
affected by the stack gas.  Leak check the system, and 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 18-9a).
Use this method whenever there is a possibility of an explosion due to
pumps, heated probes, or other flame producing equipment.
     7.1.4  Other Modified Bag Sampling Procedures.  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 temperature 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 alternative, collect the sample gas, and simultaneously dilute it in
the Tedlar bag.
     In the first procedure, heat the box containing the sample bag to
the source temperature, 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 analytical
area, keep the box heated to source temperature until  analysis.   Be sure
                                18-20

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that the Bethod of heating the box and the control for the heating
circuit are compatible with the safety restrictions required In each
area.
     To use the second procedure, prefill the Tedlar bag with a known
quantity of Inert gas.  Meter the Inert gas Into the bag according to
the procedure for the preparation of gas concentration standards of
volatile liquid Materials (Section 6.2.2.2), but eliminate the widget
Impinger 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, or Teflon positive displacement pump.  Verify the dilution
factors periodically through dilution and analysis of gases of known
concentration.
     7.1.5  Analysis of Bag Samples.  Connect the needle valve, pump,
charcoal tube, and flowmeter to draw gas samples through the gas sampling
valve.  Flush the sample loop with gas from one of the three Tedlar bags
containing a calibration mixture, and analyze the sample.  Obtain at
least two chromatograms for the sample.  The results are acceptable when
the peak areas from two consecutive Injections agree to within 5 percent
of their average.   If they do not agree, run additional samples until
consistent area data are obtained.  If this agreement Is not obtained,
correct the Instrument technique problems before proceeding.  If the
results are acceptable, analyze the other two calibration gas mixtures
in the same manner.  Prepare the calibration curve by using the least
squares method.
     Analyze the two field audit samples as described in Section 6.5 by
connecting each Tedlar bag containing an audit gas mixture to the sampling
                                 18-21

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valve.  Calculate the results; record and report the data to the audit
supervisor.  If the results are acceptable, proceed with the analysis of
the source samples.
     Analyze the source gas samples by connecting each bag to the sampling
valve with a piece of Teflon tubing identified with that bag.  Follow
the restrictions on replicate samples specified for the calibration
gases.  Record the data.  Analyze the other two bag samples of source
gas In the same Manner.  After all three bag samples have been analyzed,
repeat the analysis of the calibration gas mixtures.  Use the average of
the two calibration curves to determine the respective sample concentrations.
If the two calibration curves differ by more than 5 percent from their
mean value, then report the final results by both calibration curves.
     7.1.6  Determination of Bag Water Vapor Content.  Measure the
ambient temperature and barometric pressure near the bag.  From a water
saturation vapor pressure table, determine and record the water vapor
content of the bag as a decimal figure.  (Assume the relative himidity
to be 100 percent unless a lesser value 1s known.)
     Use the field analytical data sheet 1s shown in Figure 18-11.  The
sheet has been designed to tabulate information from the bag collection,
direct interface, and dilution interface systems; as a result, not all
of the requested information will apply to any single method.  Note the
data that do not apply with the notation "N.A."  Summarize the analysis.
     7.2  Direct Interface Sampling and Analysis Procedure.  The direct
interface procedure can be used provided that the moisture content of
the 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 with this method.
                                 18-22

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     7.2.1  Apparatus.
     7.2.1.1  Probe.   Constructed of stainless steel, Pyrex glass, or
Teflon tubing as required by duct temperature, 6.4-tnm OD, enlarged at
duct end to contain glass wool  plug.  If necessary, heat the probe with
heating 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 Mterlal.
     7.2.1.3  Quick Connects.   To connect sample line to gas sampling
valve on GC Instrument and to pump unit used to withdraw 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 temperature.
     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 GC Instrument.
     7.2.1.6  Needle Valve.   To control gas sampling rate from the
source.
     7.2.1.7  Pump-  Leak!ess Teflon-coated diaphragm-type pump or
equivalent, capable of at least 1 liter/minute sampling rate.
     7.2.1.8  Flowmeter.  Of suitable range to measure sampling rate.
     7.2.1.9  Charcoal Adsorber.  To adsorb organic 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  hydrogen for  a flame ionlzation detector (FID) if one is
used.
                                18-23

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     7.2.1.11  Gas Chrotiatograph.  Capable of being moved  Into the
field, with detector, heated gas sanpllng valve, column required to
complete separation of desired components, and option for  temperature
programmlng.
     7.2.1.12  Recorder/Integrator.  To record results.
     7.2.2  Procedure.  To obtain a sample, assemble the sampling system
as shown 1n 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 temperature as Indicated on the
thermocouple readout device, control the heating to maintain a temperature
of 0 to 3°C above the source 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 calibration gas and analyze a portion of  that gas.
Record the results.  After the calibration gas sample has  been flushed
Into the GC Instrument, turn the gas sampling valve to flush position,
then reconnect the probe sample line to the valve.  Move the probe to
the sampling position, and draw source gas Into the probe, heated line,
and sample loop.  After thorough flushing, analyze the sample using  the
same conditions 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 5 percent of their mean value, analyze
additional samples until  two consecutive analyses meet this criteria.
Record the data.  After consistent results are obtained, remove the
probe from the source and analyze 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 Information.
                                18-24

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     (Note:  Take care to draw all samples, calibration Mixtures, and
audits through the sample loop at the sane pressure.)
     In addition, analyze the field audit samples by connecting the
audit sample cylinders to the gas sampling valve.  Use the sane instrument
conditions as were used for the source samples.  Record the data, and
report the results of these analyses to the audit supervisor.
     7.3  Dilution Interface Sampling and Analysis Procedure.  Source
samples that contain a high concentration 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 that described in the Section 7.2, 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.  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 dilution apparatus.
     7.3.1  Apparatus.  The equipment required in addition to that
specified for the direct interface system 1s as follows:
     7.3.1.1  Sample Pump.  Leakless Teflon-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-150 Komhyr Teflon positive
displacement type delivering 150 cc/minute, or equivalent.  As an option,
calibrated flowmeters can be used in conjunction with Teflon-coated
diaphragm pumps.
     7.3.1.3  Valves.  Two Teflon three-way valves, suitable for connecting
to 6.4-mm OD Teflon tubing.
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     7.3.1.4  Flowmeters.  Two, for measurement of diluent gas, expected
delivery flow rate to be 1,350 cc/n1n.
     7.3.1.5  Diluent Gas with Cylinders and Regulators.  Gas can be
nitrogen or clean dry air, depending on the nature of the source gases.
     7.3.1.6  Heated Box.  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 facilitate connection
of:  (1) the heated sample line fro* the probe, (2) the gas sampling
valve, (3) the calibration gas Mixtures, and (4) diluent gas lines.  A
schematic diagram of the components and connections is shown in
Figure 18-13.
     (Note:  Care Mist 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 18-13 is 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 sampled, it may be possible to elminate the probe
heaters.  In either case, a heated Teflon line is used to connect the
heated box to the gas sampling valve on the chromatograph.
     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 chromatograph.  Vent the source
gas from the gas sampling valve directly to the charcoal filter, eliminating
the pump and rotameter.   Heat the sample probe, sample line, and heated
box.  Insert the probe and source thermocouple at the centroid of the
duct.  Measure the source temperature, and adjust all heating units to a
                                18-26

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temperature 0 to 3°C above this temperature.  If this 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.  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 gas using the
dilution factor and the calibration curves prepared in the laboratory.
Record the pertinent data on the data sheet shown in Figure 18-11.  If
the data on the diluted calibration gas are not within 10 percent of the
expected values, determine whether the chromatograph or the dilution
system 1s in error, and correct it.  Verify the GC operation using a low
concentration standard by diverting the gas into the sample loop, bypassing
the dilution system.   If these analyses are not within acceptable limits,
correct the dilution system to provide the desired dilution factors.
Make this correction by diluting a high-concentration standard gas
mixture to adjust the dilution ratio as required.
     Once the dilution system and GC operations are satisfactory, proceed
with the analysis of source gas, maintaining the same dilution settings
as used for the standards.  Repeat the analyses until two consecutive
values do not vary by more than 5 percent from their mean value are
obtained.
     Repeat the analysis of the calibration gas mixtures to verify
equipment operation.  Analyze the two field audit samples using either
the dilution system, or directly connect to the gas sampling valve as
required.  Record all data and report the results to the audit supervisor.
                                18-27

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     7.4  Adsorption Tube Procedure  (Alternative  Procedure).   It  is
suggested that the tester refer to the National Institute for  Occupational
Safety and Health (NIOSH) method  for the particular organics 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 adsorptive capacity information.
     7.4.1  Additional Apparatus.  In addition to the equipment listed
in the NIOSH method for the particular organic(s) to be sampled,  the
following items (or equivalent) are  suggested.
     7.4.1.1  Probe (Optional).  Borosilicate  glass or stainless  steel,
approximately 6-mm ID, with a heating system if water condensation is a
problem, and a filter (either in-stack or out-stack heated to  stack
temperature) to remove particulate matter.  In most instances, a  plug of
glass wool is a satisfactory filter.
     7.4.1.2  Flexible Tubing.  To connect probe  to adsorption tubes.
Use a material that exhibits minimal  sample adsorption.
     7.4.1.3  Leakless Sample Pump.  Flow controlled, constant rate
pump, with a set of limiting (sonic) orifices  to provide pumping  rates
from approximately 10 to 100 cc/min.
     7.4.1.4  Bubble-Tube Flowmeter.   Volume accuracy within +1 percent,
to calibrate pump.
     7.4.1.5  Stopwatch.   To time sampling 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 are 800/200 mg
for charcoal  tubes and 1040/260 mg for silica gel  tubes.   As an alternative,
the tubes may contain a porous polymer adsorbent such as Tenax GC or
XAD-2.
                                 18-28

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     7.4.1.7  Barometer.  Accurate to 5 mm Hg, to measure atmospheric
pressure during sampling and pump calibration.
     7.4.1.8  Rotameter.  0 to 100 cc/min, to detect changes in flow
rate during sampling.
     7.4.2  Sampling and Analysis.  It is suggested that the tester
follow the sampling and analysis portion of the respective NIOSH method
section entitled "Procedure."  Calibrate the pump and limiting orifice
flow rate through adsorption tubes with the bubble tube flowmeter before
sampling.  The sample system can be operated as a "red rail ating loop"
for this operation.  Record the ambient temperature and barometric
pressure.  Then, during sampling, use the rotameter to verify that the
pump and orifice sampling rate remains constant.
     Use a sample probe, if required.  Minimize the length of flexible
tubing between the probe and adsorption tubes.  Several adsorption tubes
can be connected In series, if the extra adsorptive capacity is needed.
Provide 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(s) of the volatile organic(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 1n the emissions, then develop relative adsorptive capacity
information.  If water vapor is present in the sample at concentrations
above 2 to 3 percent, the adsorptive capacity may be severely reduced.
Operate the gas chromatograph according to the manufacture's instructions.
                                 18-29

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After establishing optima conditions, verify and document these conditions
during all operations.  Analyze the audit samples (see Section 7.4.4.3),
then the Mission samples.  Repeat the analysis of each sanple until the
relative deviation of two consecutive injections does not exceed 5 percent.
     7.4.3  Standards and Calibration.  The standards can be prepared
according to the respective NIOSH Method.  Use a Minima of three different
standards; select the concentrations to bracket the expected average
sample concentration.  Perfom the calibration 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 Oesorption Efficiency.  During the testing
program, determine the desorption efficiency in the expected sample
concentration range for each batch of adsorption media to be used.   Use
an internal standard.  A minimum desorption efficiency of 50 percent
shall be obtained.  Repeat the desorption determination until the relative
deviation of two consecutive determinations does not exceed 5 percent.
Use the average desorption efficiency of these two consecutive
determinations for the correction specified in Section 7.4.4.5.   If the
desorption efficiency of the compound(s) of interest is questionable
under actual sampling conditions, use of the Method of Standard Additions
may be helpful to determine this value.
     7.4.4.2  Determination of Sample Collection Efficiency.   For the
source samples, analyze 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.
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     7.4.4.3  Analysis Audit.  Immediately before the sanple 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.  Perform all leak checks according to the
manufacturer's Instructions, and record the results.  Use the bubble-tube
flowmeter to measure the pump volume flow rate with the orifice used in
the test sampling, and record the result.  If it has changed by more
than 5 but less than 20 percent, calculate an average flow rate for the
test.   If the flow rate has changed by more than 20 percent, recalibrate
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 desorption efficiency (decimal value).  Report results
as ppm by volume, dry basis.
     7.5  Reporting of Results.  At the completion of the field analysis
portion of the study, ensure that the data sheets shown in Figure 18-11
have been completed.  Summarize this data on the data sheets shown in
Figure 18-15.
8.   Bibliography
      1.  American Society for Testing and Materials.  Ci Through Cs
Hydrocarbons in the Atmosphere by Gas Chromatography.  ASTM 0 2820-72,
Part 23.  Philadelphia, Pa.  23:950-958.  1973.
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      2.  Corazon, V. V.   Methodology for Collecting and Analyzing
Organic Air  Pollutants.   U.S.  Environmental  Protection Agency.
Publication  Mo.  EPA-600/2-79-042.   February 1979.
      3.  Dravnieks,  A.,  B.  K.  Krotoszynski,  J.  Whitfield, A. O'Oonnell,
and T. Burgwald.  Environmental  Science and Technology.   5(12):1200-1222.
1971.
      4.  Eggertsen,  F. T.,  and  F.  M.  Nelsen.   Gas Chromatographic
Analysis of  Engine Exhaust and Atmosphere.   Analytical  Chemistry.
30(6):  1040-1043.  1958.
      5.  Feairheller, W.  R., P. J. Nam, D.  H.  Harris,  and D. L.  Harris.
Technical Manual  for  Process Sampling Strategies for Organic Materials.
U.S.  Environmental Protection Agency.   Research Triangle Park, N.C.
Publication  No.  EPA 600/2-76-122.   April 1976.   172 p.
      6.  FR, 39 FR 9319-9323.   1974.
      7.  FR, 39 FR 32857-32860.  1974.
      8.  FR, 41 FR 23069-23072  and 23076-23090.   1976.
      9.  FR, 41 FR 46569-46571.  1976.
     10.  FR, 42 FR 41771-41776.  1977.
     11.  Flshbein, L.  Chromatography of Environmental  Hazards, Volume  II.
Elsevier Scientific Publishing Company.   New  York,  NY.   1973.
     12.  Hamersma, J. W., S. L. Reynolds, and R.  F.  Maddalone.
EPA/IERL-RTP Procedures Manual:  Level  1  Environmental Assessment.   U.S.
Environmental Protection Agency.  Research Triangle Park,  N.C.  Publication
No. EPA 600/276-160a.   June 1976.   130 p.
     13.  Harris, J. C., M. J. Hayes,  P.  L. Levins,  and  0.  B.  Lindsay.
EPA/IERL-RTP Procedures for  Level 2 Sampling and Analysis  of Organic
Materials.  U.S.  Environmental Protection Agency.   Research Triangle
Park, N.C.  Publication No.  EPA 600/7-79-033.  February  1979.  154 p.
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     14.  Harris, W. E., H. W. Habgood.  Programmed Temperature Gas
Chromatography.  John Wiley & Sons, Inc.  New York.   1966.
     15.  Intersociety Committee.  Methods of Air  Sampling and Analysis.
American Health Association.  Washington, O.C.  1972.
     16.  Jones, P. W., R. 0. Grammar, P. E. Strup, and T. B. Stanford.
Environmental Science and Technology.  10:806-810.  1976.
     17.  HcNair Han Bunelli, E. J.  Basic Gas Chromatography.  Consolidated
Printers.  Berkeley.  1969.
     18.  Nelson, G. 0.  Controlled Test Atmospheres,  Principles and
Techniques.   Ann Arbor.  Ann Arbor Science Publishers.  1971.  247 p.
     19.  NIOSH Manual of Analytical Methods, Volumes  1,  2,  3, 4, 5,
6, 7.  U.S.  Department of Health and Human Services,  National Institute
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, Government Printing
Office, Washington. D.C. 20402.  Stock Number/Price:   Volume 1 -
017-033-00267-3/S13, Volume 2 - 017-033-00260-6/S11,  Volume  3 -
017-033-00261-4/S14, Volume 4 - 017-033-00317-3/$7.25, Volume 5 -
017-033-00349-1/$10, Volume 6 - 017-033-00369-6/$9, and Volume 7 -
017-033-00396-5/$7.  Prices subject to change.  Foreign orders add
25 percent.
     20.  Schuetzle, D., T. J. Prater, and S. R. Ruddell.  Sampling and
Analysis of Emissions from Stationary Sources; I.  Odor and Total
Hydrocarbons.  Journal of the Air Pollution Control Association.  25(9):
925-932.  1975.
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     21.  Snyder, A. D., F. N. Hodgson, M. A. Kenmer and J. R. McKendree.
Utility of Solid Sorbents for Sampling Organic Emissions from Stationary
Sources.  U.S. Environmental Protection Agency.  Research Triangle Park,
N.C.  Publication Mo. EPA 600/2-76-201.  July 1976.  71 p.
     22.  Tentative Method for Continuous Analysis of Total Hydrocarbons
in the Atmosphere.  Intersociety Committee, American Public Health
Association.  Washington, D.C.  1972.  p. 184-186.
     23.  Zwerg, G.  CRC Handbook of Chromatography, Volumes I and II.
Sterna, Joseph (ed.).  CRC Press.  Cleveland.  1972.
                                 18-34

-------
I.  Hint of Bonpany
    Addrtss
    Proctss to be smpltd
    Duct or vtnt to be saopltd
    Contacts        	         Phont
II. Proctss dtscHptlon
    Raw nattrlal
    Products
    Operating cryclt
         Chtck:   Batch	Continuous	Cyclic
         Tlnlng  of batch or cyclt	
         Btst tint to ftst	
             Figure 18-1.   Preliminary survey data sheet.
                             18-35

-------
XII.  SMpUng tttt
      A.   Description
          Site description
          Duct shape and slit
          Material	
                h1ckness_	.	1nchts
          Upstrtn distance	Indus .	diameter
          OoMnstrtM dfstanca	Inchts „	dlimtttr
          S1zt of port ^._——		
          Slzo of acctss
          Huards
       I.  Proptrtlts of gis stroM
          taptraturt	.*€	•?.  Otta lourct
          Valoclty	^  Datasoureo
          Static prtsaurt _1ncht$ HjO. Data sourea
          NoUturt conttnt	1. Data sourea
          Partlculata contant	, Data sourea
          fiasaous coaponants
                "2
                CO.
                cog.
Hydrocarbons	ppai
           Hydrocarbon coapontntx
                                          PP"
                                          PP
                                          PPi
                                          OP*
      Flgurt 18-1  (ttntlnuad).  PrtHarintry survey data sheet.

                              18-36

-------
C.  Stapling consldtrttlons
    Location to set up CC
    Special hazards to bt considered
    Power available at duct _
    Power avallabla f or 6C 	
    Plant safety requirements
    Vthlclt traffic rults
    Plant antry ttqulrawtnts
    Stcurlty a grttmnts
    Pottntlal probl
D.  Site diagrams.  (Attach additional  sheets If required).

    Figure 18-1 (continued).  Preliminary survey data sheet.
                            18-37

-------
Components to b« inalvtad    Expected concentration
 Suggtstftd chromatographic  eolvm
 Colon flow rat*    ml/min  Btad praiatir«__ jm, Hg
 Colon t«ap«ratar«t
            rrnul           *C
                 from _ ,•€ to _ ^»C at _ »C/min
 Injactlon port/«aapl« loop tcapcratax*       *C
 Datactor flow rataat Hydrogen
                               haad preiaura     nm Hg
                    Air/Oxygen      al/min,
                               n«ad pressure     ma Hg
       •p««d ^^ i»ch«»/Wnut«
          datai
      Compound     Rtttntlon tiam    Attanuation
         18-2.   Chronatographic conditions  data  sheet.
                       18-38

-------
             Calibration Curva Data - Volatile and
           Liquid Samples Collected in a Tedlar Bag
                                         Mixture
                                 Blank     1
fiM of Tedlar bag   (liters)
Dilution gas (name)
Vol. of dilution gas (liters)
Component (name)
volume of component  (ml)
Average meter tamp.  (*C)
Average mater pretture  (am)
Atnoipheric pressure (nm)
Density of liquid component
  (g/ml)
Staple loop volume (ml)
Staple loop temp. (*C)
Carrier gas flow rate  (ml/min)
Column temperature
     initial CO
     program rate (•C/ain)
     final (*C)
Injection time (24 hr. basis)
Distance  to pea*  (cm)
Chart ipeed  (cm/min)
Retention tin* (min)
Calculated concentration  (ppa)
Attenuator setting
Ptak height (MB)
toak area (ma2)
Area x attenuation
Wot peak area x attenuation against concentration to  obtain
calibration curve.
        Figure 18-3.- Calibration curve data sheet - Injection
                  of volatile sample Into Tedlar bag.
                              18-39

-------
Gas ttsed	
Method:  Bubble eater       Splroewter	Met ttst eater.
totaeater construction.
Float type
Laboratory temperature  (T obs.)	•€	*F
Uboratonr prtssurt  (P  obi.)    	In Hg          •§ Ng
                                                     Row rate   h
1,  . nox»ettr reading T1»e  («1n)  6as voluaa*  Oab conditions)0
1  Vol. of gas Bay be •easurad 1n »m 111 tars, liters or cubic feet.
b  Convert to Standard conditions (20^ C and 760 m Hg).

                    n    .0     760 x T obs. 1/2
                    **STO  Hobs  P obs. x 20

    FIQuarter reading                       How fate (STD conditions)
 Plot a»ter reading against flow rate (std) and draw smooth curve.

            Figure 18-4.  Rotaneter calibration  data  sheet.
                              18-40

-------
00
I
-fc.
                 SINGLE-STAGE CALIBRATION
                    GAS DILUTION SYSTEM
           COMPONENT
             GAS
           CYLINDER
            DILUENT
             GAS
            CYLINDER
      o
CALIBRATED ROTAMETERS
 WITH FLOW CONTROL
     VAlVES '<
                 "T" CONNECTOR
                                                TEDLAR BAG
                            FIGURE 18-5.

-------
              TWO-STAGE DILUTION APPARATUS
                               HIGH.
                            CONCENTRATION
                               WASTE
00
I
ro
             ROTAMETERS
                                  iNEEDLE VALVES
                                         _L
                             PR ) PRESSURE REGULATORS ( PR
                         DILUENT AIR
DILUENT AIR
      PURE SUBSTANCE OR
   PURE SUBSTANCE/N2 MIXTURE
                               FIGURE 18-6.
                 LOW
             CONCENTRATION
                 GAS

-------
1.  High concentration  as mixture

          Component _________ Concentration 	ppm

          Diluent gas .__^_

2.  Dilution and analysis  ata                  Date
                                 Mixture 1  Mixture  2   Mixture 3
Component gas-rotameter reading  ^^^^^^
Diluent  gas-rotameter reading    ——-—  —_   ____
Ambient  temp.  («C)                 '          ~~~"   	
Manometer reading,  inches R20            ""          —   ——*_
Flow rate component gas (ml/min)        . *           "   "
Flow rate diluent gas (ml/min)           "  ^^^~^~   	

          Stage  2

Component gas-rotameter reading  	  	
Diluent  gas-rotametex reading            *           "           "
Flow rate component gas (ml/min)         "           "           ""
Flow rate diluent gas (ml/min)           "~          ""          ~*
Calculated concentration (ppm)           "           "   	
         Analysis
Sample loop volume (ml)           	  	 	
Sample loop temp.  (•€)                    "           " """"""
Carrier gas flow rate (ml/min)     _                 " ~~~
Column temperature
     initial  («C)                 	  	 	
     program  rate  (*C/min)        	  	
     final  (»o                   zzzm  zzzzn!! —
Injection time  (24-hr.-  basis)    ZHUZZ  ZZIZIII 	
Distance to peak (inches)        	  	 	
Chart speed  (inch/min)            	  	 "
Betention time  (min)              "          ZZZZZZ
Attenuator factor                 _____  	 	
Peak height  (mm)                  __           " 	
Hak area  (mm2)                   ____           " 	
Area x attenuation factor (mm2)  _____  	 	
Plot peak area  x attenuator factor against concentration  to
ottilir calibration curve.
Figure* 18-7.  Calibration curve data sheet -
              ion
                        dilution method.

-------
3.  Low Concentration standard
          Knevn concentration  (ppm)	
          Retention time  (min)          	_
          Injection time  (24-hour basis)  ^ ____
          Attenuation factor            _____
          Peak height (•)              	
          Peak area (BJ?)                ___
          Peak area x attenuation (sa2)   ___
          Calculated concentration (ppm)
          Deviation (I)                 	
4.  Audit samples                            Sample 1   Sample 2
          Retention tiae  (min)               _—^.^   ——
          Injection tiae  24-hour basis)        __   	
          Attenuation factor                 ___   —
          Peak height («0                   ^_   	
          Peak area  (eV)                   	   	
          Peak area x attenuation factor          __   «___^_
          Measured concentration            ____«.   ___
          Data reported on  (date)           __   -	
          Data reported by  (initial)        __   __^__,
          .Certified concentration (ppm)      «_«_   —_
          Deviation (%)                      	   	
 •otes   If a .pump  is used instead of a rotameter for component gas
        flow,  substitute  pump delivery rate for rotameter  readings)

               Figure 18-7 Continued). Calibration curvt data sheet -
                                dilation mthod.
                                    18-44

-------
        APPARATUS FOR PREPARING STANDARD GAS MIXTURES
co
i
01
         NITROGEN
         CYLINDER
                                         SYRINGE
DRY GAS
 METER

   BOILING
  WATER BATH
                              TEDLAR BAG
                              CAPACITY
                              50 liters
                          FIGURE 18-8.

-------
                    INTEGRATED BAG SAMPUNG TRAIN
          FILTER
       (GLASS WOOL)
00
I
-P»
CTl
STACK WALL      TEFLON
            SAMPLE  LINE

  PROBE
                                  BALL
                                 CHECKS
                     NO,
                   CHECKS
                            QUICK
                           CONNECTS
                            FEMALE
                         TEDLAR OR
                         ALUMINIZED
                         MYLAR BAG
                          VACUUM LINE
                           NEEDLE
                            VALVE
                                   RIGID LEAK-PROOF
                                      CONTAINER
                               CHARCOAL
                                 TUBE
 FLOW
METER
                           PUMP
                                   FIGURE 18-9.

-------
EXPLOSION  RISK  GAS SAMPLING METHOD
                *
               PINCH
               CLAMP
             GROMMET
                          FLOWMETERg
                    A,
                    ' SAMPLE
                         V
                      BAG
                     AIR TIGHT STEEL DRUM
                                  ] C
  DIRECTIONAL
 NEEDLE VALVE
                                       QUICK DISCONNECTORS
EVACUATED STEEL DRUM
                     FIGURE 19-9a.

-------
Mint
Sltt
                         Sarolel        Saaple 2        Sample  3
Source temperature (*C)
Barometric pressure (M
Ambient temperature (*C)
Sa*p1t flow rate(appr.)
Bag
Start
Finish tie*
           Flgurt 18-10.  Field swplt data shttt - Ttdlar
                      bag colltctlon Mthod.
                            18-48

-------
Hint                                       Data.
Location	
1.  Ganaral information
          Sourea tamparatura  (*C)
          Froba tamparatura  CO
          Ambient tamparatura (*C)
          Ataospbarie praasura (mm)
          Source preasura  (*Bg)
          Abaoluta aourca praaaura (BOB)
          Sampling rata  (litar/min)
          Saapla loop voluna  (ml)
          Saapla loop taaparatura (*C)
          Columnar  tamparaturat
                Initial (•O/tiaa (min)
                Program ratt  (•C/min)
                Final (•C)/t1m (ain)
          Carriar gaa flow rata (ml/min)
          Oataetor  tamparatura (*C)
          Znjaetion tima (24-hour basis)
          Chart apaad (mm/min)

          Dilution  gas flow rata  (ml/min)
          Dilution  Gaa uaad  (aymbol)
          Dilution  ratio
                Figure 18-11.  Field analysis data sheets.
                              18-49

-------
2.  Tiald Analysis Data • Calibration Gas
    Bun Mo.               «Jaa
    Component*   Araa    Attenuation   A x A Factor   Cone, (ppm)
    Bra Bo.               Tiaa
    Component*   Araa   Attanuation   A x A Factor   Cone,  (ppm)
    tan Mo.	    Ti»a
    Componants   Araa   Attenuation    A x A Factor   Cone.  (ppn>)
              Flgurt 18-11 (tontlnutd).  Fltld analysis data shtits.
                                  18-50

-------
        DIRECT  INTERFACE  SAMPLING  SYSTEM
STACK WALL
£  GLASS
i,  WOOL
1/2-in.
TUBING
                   T C
                 READOUT
       /
        1/4-in.
        SS TUBING
              r
                        LI
               TEMPERATURE
               CONTROLLER
                                   T C
                                 READOUT OR
                                 CONTROLLER
                       INSULATION
                                  HEATED TEFLON
                                     LINE
                                                HEATED
                                         VALVE IN G C
                                                   NEEDLE
                                                   VALVE
                                                            FLOWMETER

                                                           CHARCOAL
                                                           ABSORBER
i
                                                       PUMP

                                                        TO G C INSTRUMENT
                                                    *-CARRIER IN
                               FIGURE 18-12.

-------
                  DIAGRAM  OF THE  HEATED BOX
         REQUIRED  FOR  DILUTION  OF  SAMPLE GAS
                            VENT TO CHARCOAL ADSORBERS
00
I
tn
ro
HEATED LINE
FROM PROBEc
                 QUICK
                CONNECT
-e
SOURCE GAS
 PUMP 1.5
  l/m1n
 750
cc/mln
                                   10:1   100:1
                                            QUICK CONNECTS TO
                                            GAS SAMPLE VALVE
                                              150
                                             cc/m1n
                          PUMP
                                3-WAY VALVES
                                 IN 100:1
                                 POSITION
                              CHECK VALVE QUICK
                                         FLCWMETERS
                                        (ON OUTSIDE
                                          OF BOX)
                                 I
                            CONNECTS FOR CALIBRATION    FLOW RATE QFlL^J
                       	1350jcc/m1n^  I	

                          HEATED BOX AT 120°C OR SOURCE TEMPERATURE     'i'
                                 FIGURE 18-13.

-------
       Gasaotis Organic Saapling and Analysis Check List
        (Respond with initials or number as appropriata)

1.  Presurvay data                                         Datt
         A.  Grab sample collected                  PH
         1.  Grab saapla analyxad for composition  PH
                   Hathod  GC                       I  I
                           GC/MS
                           Othar
         C.  'GC-7ZD analysis parformad
2.' Laboratory calibration  data
         A*  Calibration eorvas praparad
                   Munbar  of conponants
                   Nunbar  of concentrations/
                      componant  (3  raquirad)
         B.  Audit saoplas (optional)
                   Analysis  compl«tad               |  I
                   Varif lad  for concantration
                   OX obtalnad  for f laid work
3.  Sampling procaduras
          A.  Mathod
                    Bag saapl*                       j   I
                    Diract intarf aca
                    Dilution intarfaea
          B.  Nuabar of sanplas collactad
4.  Fiald Analysis
          A.  Total hydrocarbon analysis parfonnad
          B.  Calibration curva praparad
                    Vuabar of conponants
                    Hunbar of concentration*  par
                      conponant  (3 raquirad)

            Figure  18-14.  Sampling and analysis check.
                             18-53

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Plant
                 Gaseous Organic Sampling and Analysis Data


                                                  Data
Location
00
I
en
                                          Source          Source          Source
                                         tample 1        «asj1t  2        «aan1a  3
1.  General Information

    Source temperature  (*C)
    Probe temperature  <*C)
    Ambient, temperature  (*C)
    Atmospherio pressure (m Hg)
    Source pressure (na Hg)
    Sampling rat*   (ml/»in.)
    Sample loop volime  |M!|
    Sample loop temperature  (*C)
    Sample collection  time  (24-hr, baaia}
    Column temperature
      Initial  CC)
      Program  rate (•C/min)
      Pinal  («C)
    Carrier gas flow rate (ml/min
    Detector temperature (*C)
    Chart speed (cn/min.)

    Dilution gas flow  rate  (ml/min.)
    Diluent gas used  (symbol)
    Dilution ratio
                                      Performed by (signature)i.
                                                          Datet
                   Figure 18-14.   Sampling and analysis sheet,

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 48344     Federal  Register /' Vol.  48, No. 202 / Tuesday.  October 18. 1983  /  Rules and  Regulations
  5. In Appendix A of Part 60, Method
18 is added as follows:

Method 18—Measurement of Gaseous
Organic Compound Emissions by Gas
ChrouMtography

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 potentially
explosive atmospheres.]
1. Applicability and Principle
  1.1  Applicability. This method applies to
the analysis of approximately 90 percent of
the total gaseous organic* 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) can polymerize before analysis.
or (3) have very low vapor pressures at stack
or instrument conditions.
  1.2  Principle. This method is based on
separating the major components of a gas
mixture with a gas chramatograph (GC) and
measuring the separated components with a
suitable detector.
  The retention times of each separated
component are compared with those of
known compounds under identical
conditions. Therefore, the analyst confirms
the identity and approximate concentrations
of the organic emission component*
beforehand. With this information, the
analyst then prepares or purchases
commercially available standard mixtures to
calibrate the CC under conditions identical to
those of the samples. The analyst also
determines the need for sample dilution to
avoid detector saturation, gas stream
filtration to eliminate participate 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
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.
  2-2   Sensitivity. The sensitivity limit for a
compound is defined as the minimum
detectable concentration of that compound
or the concentration that produces a signal-
to-nois* ratio of three to one. The minimum
detectable concentration is determined '
during  the prasurvey calibration for each
compound.
3. Precision and Accuracy
  Gas chromatographic techniques typically
provide a precision of 5 to 10 percent relative
standard deviation (RSD). but an experienced
GC operator with  a reliable instrument can
readily achieves percent RSD. For this
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
preparation values.
  Resolution interferences Ujat 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 tht use of temperature
programming.
 -The analytical system is demonstrated to
be essentially free from contaminants by
periodically 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
eliminate errors in concentration calculations
due to  the volume of water vapor in the
samples, moisture concentrations are
determined for each sample, and a correction
factor is applied to any sample with greater
than 2  percent water vapor.
5. Presurvey and Presurvey Sampling
  A presurvey shall be performed on each
source to be tested. The purpose of the
presurvey is to obtain all information
necessary to design  the emission test. The
most important presurvey data are the
 average stack temperature and temperature
 range, approximate particulate concentration.
 static pressure, water vapor content, and
 identity and expected concentration of each
 organic compound to be analyzed. Some of
 this information can be obtained from
 literature surveys, direct knowledge, or plant
 personnel. However,  presurvey samples  of
 the gas shall be obtained for analysis to
 confirm the identity and approximate
 concentrations of the specific compounds
 prior to the final testing.
  5.2  Apparatus.
  5.1.1  Teflon Tubing. (Mention of trade
 names or specific products does not
 constitute endorsement by the U.S.
 Environmental Protection Agency.) Diameter
 and length determined by connection
 requirements of cylinder regulators and the
 GC. Additional tubing is necessary to connect
 the GC sample loop to the sample.
  5.1.2  Gas Chromatograph. GC with
 suitable detector, columns, temperature-
 controlled sample Ibop and valve assembly,
 and temperature programable oven, if
 necessary. The GC shall achieve sensitivity
 requirements for the compounds unde* study.
  5.1.3  Pump. Capable of pumping 100 ml/
 min. For flushing sample loop.
  5.1.4 Flow Meter.  To accurately monitor
 sample loop flow rate of 100 ml/min.
  5.1 J  Regulators. Used on gas cylinders
 for GC and for cylinder standards.
  5.1.8  Recorder. Recorder with linear strip
 chart is m'n'""'m acceptable. Integrator
 (optional) is recommended.
  5.1.7  Syringes. 1.0- and 10-microliter size.
 calibrated, maximum accuracy (gas tight) for
 preparing standards and for injecting head
 space vapor from liquid standards In
 retention time studies.
  5J.S Tubing Fittings. To plumb GC and
 gas cylinders.
  5.1.9  Septums. For syringe injections.
  5.1.10  Glass Jars. If necessary, clean-
 colored glass jars with Teflon-lined lids for
 condensate sample collection. Size depends
 on  volume of condensate.
  5.1.11 - Soap Film Flow Meter. To
 determine flow rates.
  5.1.12  Tedlar Bags. 10- and 50-liter
 capacity, for preparation of standards.
  5.1.13  Dry Gas Meter with Temperature
 and Pressure Gauges. Accurate to ±2
 percent for perparation of gas standards.
  5.1.14  Midget Impinger/Hot Plate
.Assembly. For preparation of gas standards.
  5.1.15  Sample Flasks. For presurvey
 samples, must havs gas-tight seals.
  5.1.16  Adsorption Tubes. If necessary,
 blank tubes filled with necessary adsorbent
 (charcoal. Tenax, XAD-Z. etc.) for presurvey
 samples.
  5.1.17  Eersonnel Sampling Pump.
 Calibrated, for collecting adsorbent tube
 presurvey samples.
  5.1.18  Dilution System. Calibrated, the
 dilution system is to be constructed following
 the specifications of an acceptable method.
  5.2  Reagents.
  5.2.1 Deionized Distilled Water.
  5.2.2 Methylene Dichloride.
  6.2.3 Calibration Gases. A genes of
 standards prepared for every compound of
 interest.
                                                            1S-5E

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           Federal Register  /  Vol. 48. No. 202 / Tuesday. October  18.  1983  /  Rules and Regulations
  5.2.4  Calibration Solutions. Simples of all
the compounds of interest in • liquid form, for
retention time studies.
  5.2J  Extraction Solvents. For extraction
of adsorbent rube samples in preparation for
analysis.
  5.2.6  Fuel As recommended by the.
manufacturer for operation of the CC
  5.2.7  Carrier Gas. Hydrocarbon free, as
recommended by the manufacturer for
operation of the detector and oompatability
with the column.
  5.2J  Zero Gas. Hydrocarbon free air or
nitrogen, to be used for dilutions, blank
preparation, and standard preparation.
  5-3 S+T'lfr'B
  5 J.I  Collection of Samples with Glass
Sampling Flasks. Presorvvy •ample* can be  -
collected in predeaned ZSO-nu-double-ended
glass sampling. flasks-Teflon stopcocks.
without frease. are preferred. Flasks should
be cleaned as follows: Remove the stopcocks
from both end* of the flasks, and wipe the
parts to remove any grease, dean the
itopcocks. barrels, and receiver* with
methylene dichloride. Clean all glass ports
with a soap sotetkm. then rinse with tap and
deiooixed distilled water. Place the flask to a
cool glass annealing furnace aad apply heat
up to SOT CMatatam at this temperature for
 1 hoar. After tUa tiM period. «bat off mod
 open the fumeos to •Dow the flask to cooL
 Grease the stopcocks wlm stopcock greese-
 and return them to the flask receiver*. Purge
 the assembly with Uejh-Daritjr nitrogen far 2
 to  S minutes. Ooee off the stopcocks after
 purging to maintain a aught positive nitrogen
 pressure. Sean the stopcocks with tape,
   Presurvey asjnples can be obtained either
 by drawing the ga*a« mttHhe previously
 evacuated flask or by drawing the geses into
 and paging the flask with a rubber soction
 bulb.
   54.1.1  Eracaated Flask Procedure. Use a
 high-vacuum pnssp to evacuate the Bask-to
 the capacity of the poop, then don off the
 stopcock hefting to the pomp. Attach a e-asm
 outside diameter (OQ) glass tee to the flask
 inlet with a short piece of Teflon robing.
 Select a 6-mm OD borasilicate sampling   ,
 probe, enlarged at one end to a 12-mm OD
 and of sufficient length to reach the centroid
 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 toning. Connect a rubber suction
  bulb to the third leg of the tee. Place the filter
  end oTneixobe at the centroW of the duct
  and purge fee probe wtth the robber suction
  bulb. After tne probe is completely purged
  and filled with doct gases, open the stopcock
  to the grab Bask until the pressure in the
  flask leaches duct pressure. Close off the
  stopcock, and remove the probe from the
  duct Remove the tee from the flask and taps
  the stopcocks 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 Section
  54.1.1. Place the filter end of the probe at die
  centroid of the duct and apply suction with
  the bulb to completely purge the probe and
 flask. After the flask has been purged, close
 off the stopcock near the suction 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 pussure.
   5.3 3.  Flexible Bag Procedure. Tedlar or
 alurainized Mylar bags can also be used to
 obtain the presurvey sample.  Use new bags.
 and leek check them before field use. In
 addition, check the beg before use for  -
 contamination by filling it with nitrogen or
 air, and analyzing the gas by  GC at high
  sensitivity. Experience indicates  that it is
  desirable to allow the inert gas to remain in
"the bag about 24 BOUTS or longer  to check for
  desorption of organic* from the beg-PoBow
  the leak check and sano^e collection
  procedures given in Section 7X            ^
    SJJ  Deteiuunetton of Moisture Content
  For combustion or water-controlled
  proceeses, wrtaiii tne luoialyte I»^H»HH iweu
  plant personnel or by laiieieniUBt during
  the presurvey. If the source to below ST C.
  measure the wet bulb end dry bulb
  tempeiauaes, end cakuleto the moisture
  content using a psychfometric chart At
  higher leu«eratnrea, use Method 4 to
                                           6.1.3  Preparation of Presurvey Samples. If
                                         the samples were collected on an adsorbent
                                         extract the-sample a* recommended by the
                                         manufacturer for removal of the compounds
                                         with e solvent suitable to the type of GC
                                         analysis. Prepare other samples in an
                                         appropriate manner.
                                           6.1.4  Presurvey Sample Analysis. Before
                                         analysis, heat the presnrvey 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 sampies that
                                         contain the components expected to be in tht
                                         stream. H any couBound* cannot be
                                         identified with certainty by this procedure.
                                         identify them by other mean* such as GC/
                                         mass speetrosoopy tCC/MS) or GC/inirared
                                          techniques. A CC/MS sjitoiu at
  54  Determination of Static!
ObtaaNhe static piusmu from the plant
personnel or measurement If a type S print
tube and an tocnned ssanooeter ereueeu,
take can to angn the pttot tnbe W fronrthe
direction of the flow. Disconnect one of,me
tubes to tne ssenosseter. and reed the static
pressure: note whether the reeding is positive
or negative,
  5.6  Collection of Preeervey
Adsorption Tnbe. Fouo Section 7 A
                                     win
6. AnaJyga Dt ia/qBm«nf
  Piesui»ey samples ahatt be need to develop
and confimfme beet-eampung and analysis
    6.1  Selection of PC
    6,1.1  r
               TTinina Fainfl im Thii tr1*1?'
contact with plant pmsoonel oouceiuing the
plant process and the anttcipeled emission*.  x
choose a column that provides good
resolution end rapid analysis time. The
choice of en appropriate column can be aided
by a literature search, contact wlm
manufacturers of CC nohiume, and discussion
with penonuel at the i
  records of then- prodncts. Their t
  service departments mey be abb to
  recommend appropriate catenas and
  detector type for seperating the eatidpated
  compounds, and they may be
  mfortMtion en iut
                          abtetoprovide
operating conditions, and colemn limitations.
  Plants with analytical laboratories may be
able to provide ^formation on their
analytical pruceduies. inchxting extractions.
detector type, column types, compounds
emitted, and approximate concentrations.
  6.1.2  l>reliminaryGC Adjustment Using
the standards and column obtained in
Section 6.1.1. perform initial tests to
dertermine appropriate GC conditions that
provide good resolution and minimum
analysts time for the compounds of interest
  Use the CC conditions determined by the
procedures of Section 8X2 for the first
injection. Vary the GC parameters during
subsequent injection* to determine the
optimum settings. Once the optimum settings
have been determined, perform repeat
injections of the sample to determine the
retention time of each compound. To inject a
sample, draw sample through the loop at a
constant rate (100 ml/nun for 30 seconds). Bs
careful not to pressurize the gas in the loop.
TumoffthepompandaMowthegasinthe
•ample loop to come to ambient pressure.
Activate ft* sample valve, and record
injection time, loop lenperatnre, column
temperature, carrier flow rate, chart speed
and attenuator setting. Calculate the
retention mne of each peak using the
distance fromJejecnWrn the peak maximum
divided by the chart speed. Retention time*
should be lepeatabU within OS seconds.
  If the concentration* an too Ugh for
appropriate detecte response, a smaller
sample loop or dOnnons may be need for gas
samples, and. far Uatnd samples, dilation
with solvent is appropriate. Use tne standard
curves (Section 6J) to obtain an estimate of

  Identify afl peeks.by comparing the known
retention times of compounds expected to be
in the retention times of peaks in the sample.
Identify any remaining unidentified peaks
which have areas larger than S percent of the
total using a CC/MS, or estimation of
possible compounds by their retention times
compared to known compounds, with
confirmation, by further GC analysis.
  &2  Calibration Standards. If the
presurvey samples an collected in an
adsorbent tube (charcoal. XAD-t Tenaic.
etc.), prepare the standards in the same
solvent used for the" extraction procedure for
the adsorbent Prepare several standards for
each compound throughout the range of the
sample.
  &2.1  Cylinder Calibration Geses. If
available, use NBS reference gases or
commercial gas mixtures certified through
direct analysis for the calibration curve*.
  6.2.1.1  Optional Cylinder Approach. As
an alternative procedure, maintain high and
low calibration standards. Use the high
concentration (50 to 100 ppm) standard to
prepare e three-point calibration curve with
an appropriate dilution technique. Use this
                                                          18-56

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48346     Federal Register  / Vol.  48, No. 202 /  Tuesday.  October 18,  1983  / Rules  and  Regulations
same approach also to verify the dilution
techniques for high-concentration source
gases.
  To prepare the diluted calibration samples.
use calibrated rotameters  to meter both the
high concentration calibration gas and the
diluent gas. Adjust the flow rates through the
rotameters with micrometer valves to obtain
the desired dilutions. A positive displacement
pump or other metering techniques may be
used in place of the rotameter to provide a
fixed flow of high concentration gas.
  To calibrate the rotameters. connect each
rotameter between the diluent gas supply and
a suitably sized bubble meten spirometer. or
wet test meter. While it is desirable to
calibrate the calibration gas flowmeter with
calibration gas. generally  the available
amount of this gas will preclude it. The error
introduced by using the diluent gas is
insignificant for gas mixtures of up to 1,000 to
2.000 ppm of each organic component. Record.
the temperature and atmospheric pressures
as follows:
         .0,-Q
            1/2 Eq. 18-1
C.-
                         Eq. 18-2
                                 and 10 percent goes to the second stage
                                 flowmeter. Fill the Tedlar bag with the dilute
                                 gas from'the second stage. Record the
                                 temperature, ambient pressure, and water
                                 manometer pressure readings. Correct the
                                 flow reading in the first stage as indicated  by
                                 the water manometer reading. Calculate the
                                 concentration of the component in the final
                                 gas mixture as follows:
 Where:
 Qi = Flow rale at new absolute temperature
    (Ti) and new absolute pressure (Pi).
 Qi = Flow rate at calibration absolute
    temperature (Ti).and absolute pressure
    (P.).                .      -    ,    ,
 Connect the rotameters to the calibration and
 diluent gas supplies using 6-mm Teflon
 tubing. Connect the outlet side of the
 rotameters through a connector to a leak-free
 Tedlar bag as shown in Figure 18.S. (See.
 Section 7.1 for leak check procedures.) Adjust
 the gas flows to provide the desired dilution.
 and flll the bag with sufficient gas for
 calibration. Be careful not to fill to the point
 where it applies additional pressure on the
 gas. Record the flow rates of both rotameters,
 the ambient temperature, and atmospheric
 pressure. Calculate the concentration of
 diluted gas as follows:
 Where:
. C.=Concentration of component "9" in ppm.
 Jf.=Mole fraction of component "a" in the
     calibration gas to be diluted.
 q.=Flow rate of the calibration gas contains
     mg component "a" at measured
     temperature and pressure.
 c* = Diluent gas flow at measured
     temperature and pressure.
 Use single-stage dilutions to prepare
 calibration mixtures up to about 1:20 dilution
 factor. For greater dilutions, use a double
 dilution system. Assemble the apparatus, as
 shown in Figure 18-6, using calibrated
 flowmeters of suitable range. Adjust the
 control valves so that about 90 percent of the
 diluted ga» from the first stage is exhausted.
                                                                   Eq. 18-3
Where:
C.=Concentration of component "a" in ppm.
X,=Mole fraction of component "a" in
    original gas.
q.l = Flow rate of component "a" in stage 1.
q.2=Flow rate of component "a" in stage 2.
q4l = Fk>w rate of diluent gas in stage 1.
q«2=Flow rate of diluent gas in stage 2.
  Further details of the calibration methods
for rotameters and the dilution system can be
found in Citation 21 in Section 8.
  B.Z2  Preparation of Standards from
Volatile Materials. Record all data shown on
Figure 18-3.           .-
  8^2.1  Bag Technique. Evacuate a 10-liter
Tedlar bag that has passed a leak check (see
Section 7.1). and meter in 5.0 liters of nitrogen
through a OJ> liter per revolution dry test
meter. While the bag is filling, use a 0.5-ml
syringe to inject a known quantity of the
material of interest through the wall of the
bag or through a septum—caped tee at the
bag inlet. Withdraw the-syringe needle, and
immediately cover the resulting hole with a
piece of masking tape. In a like manner.
prepare dilutions having other
concentrations. Prepare a minimum of three
concentrations. Place-each bag on a smooth
surface, and alternately depress opposite
sides of the bag 50 times to mix the gases.
Record the average meter temperature, gas
volume, liquid volume, barometric pressure.
and meter pressure.
   Set the electrometer attenuator to the XI
Position. Flush the sampling loop with lero
helium or nitrogen, and activate the sample
valve. Record the injection time, sample loop
temperature, column temperature, carrier gas
flow rate, chart speed, and attenuator setting.
Record peaks and detector responses that
occur in the absence of any sample. Maintain
conditions. Flush the sample loop for 30
seconds at the rate of 100 ml/min with one of
the calibration mixtures, and open the sample
valve. Record the injection.time. Select the
peak that corresponds to the compound of
 interest. Measure the distance on the chart
 from the injection time to the time at which
 the peak maximum occurs. Divide this-
 quantity by the chart speed, and record the
 resulting value'as the retention time.
   6.2.2.2   Preparation of Standards from less
 Volatile Liquid Materials. Use the equipment
 shown in Figure 18-8. Calibrate the dry gas
 meter with a wet test meter or a spirometer.
-Use a water manometer for the pressure
 gauge and glass, Teflon, brass, or stainless
 steel for all connections. Connect a valve to
 the inlet of the 50-liter 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 water
to reach boiling. Connect the bag to the
impinger outlet. Record the initial'meter
reading, open the bag inlet valve, and open
the cylinder. Adjust the rate so that the bag
will be completely filled in approximately 15
minutes. Record meter pressure, temperature.
and local barometric pressure.
  Fill the syringe to the desired liquid volume
with the material to be evaluated. Place the
syringe needle into the impinger inlet using
the septum provided, and inject the liquid
into the flowing 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.
  Complete filling of the bag; note and record
the meter pressure and temperature at regular
intervals, preferably 1  minute.
  When the bag is filled, stop the pump, and
close the bag inlet valve. Record the final
meter reading.
  Disconnect the bag from the impinger
outlet, and set it aside for at least 1 hour to
equilibrate. Analyze the sample within the
proven life period of its preparation.
  8.2^.3  Concentration Calculations.
Average the meter temperature (TJ and
pressure (PJ readings over the bag filling
process.
   Measure the solvent liquid density at room
temperature by accurately weighing a known
volume of the material on an analytical
balance to the nearest 1.0 milligram.  Take
care during the weighing to minimize
evaporation of the material. A ground-glass
stoppered 25-ml 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 2CTC may be used
   Calculate the concentration of material in
 the sample in mg/liter at standard conditions
 as follows:
                                                                                                                 Eq. 18-
                                                                                                                    4
                  .
 Where:   -
 CM ..i« Standard solvent concentration, mg/
     std liter.
 L,« Liquid volume injected, ml.
 p.Liquid density at room temperature, g/ml.
 T. * Meter temperature, *C
 M,.M,=Final and initial meter reading, liters.
 PM-Local barometric pressure (absolute).
     mmHg.
 P.-Meter pressure (gauge), mm Hg.
    8.3  Preparation of Calibration Curves.
 Obtain gas standards as described in Section
 6.2 such that three concentrations per
 attentuator range are available. Establish
 proper GC conditioning, then flush the
 sampling loop for 30 seconds at a rate of 100
 ml/min. Allow the sample loop pressure to
 equilibrate with atmospheric pressure, and
 activate the injection valve. Record the
  standard concentration, attentuator setting.
  injection time, chart speed, retention time.
                                                             18-57

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           Federal  Register / Vol. 48, No. 202 / Tuesday.  October 18, 1983 / Rules and  Regulations     48347
peak area, sample loop, temperature, column
temperature, and carrier gas flow rate.
Repeat the standard injection until two
consecutive injections give area counts
within 5 percenfof their average. The
average multiplied by die attenuator setting
is then the calibration area value for that
concentration.
  Repeat this procedure for each standard.
Plot concentrations along the abscissa and
the calibration area values along the •
ordmate. Perform a regression analysis, and
draw the least squares line.
  6.4  Optional Use of Prepared Cyhnders
for Dilution Calibration Checks, and
Response Factor Determinations. A set of
three standards of the major component in
the emissions is required. This set of
standards can be taken toto the field and
thereby replace the need to prepare
standards as described to Section aZz.
  The high concentration atanoura can he •
nm through toe dilution system to assess the
accuracy of the system. First, prepare a
calibration curve using the three standards
following the procedure described SB Section
m  Thnn prnfisri i illliin umpls sslnlHn
high concentration standard so that the dilute
sampk wfll IsB tfHttta the lower hasita of the

  gtf. M,t Aa^la^BA **	->*•- *-	U_	m
  IWXL WMUJTM tuts 0189 MUttfttt* ma

tost CtubteTOQQ CBfW tV CMKftDM IB StKtKHK
U. The dihrte aoBCsntmtton caicuktod from
the analyst shsJl be wittte 10 percent of the


error in the dilution system, and mmJiIti
  The calibration carrefnn the cyhnder
standards for a stosjs organic can also be.
related to me GC response carrssofan th*
 ftznA flanflana^uulvt* Asm
be used, us* the dfaect tossr^ ntethod. If
Htf flffuTftfr Pzsft*^ TffpitT^ fflflltrezti 1(t9% 4t
QUBtlOB attlVnMal 4HM CI|H*V t&s$ M( •"•!••*
OTttdaWtptlOB talMa** Tot CanOJOal D0tWMB
the** two tsi'hnliniii wfll depend on me
pnysjoal layout or ine stte. tne nttirpe   .
temperature, and the storage staUUiy of As
compounds if coflectodJa the bag, ftennjls
polar compounds by direct interfacing or
                                            edsorptiononthel
                                              7J  totes^UMl Bag Samphng and Analysis
                                              7.1J  Evacuated Cmilalmi Tlanijillin
                                            Piucedur*. la tttt* unnjedure, the begs are
 container holding the bag*. Therefore, check
 both the begs and the container for leaks
 before and after nee as fallow*: Connect e

 between the bag or rigid container and a
 P*fUMlf9 MMITGQ. PnMQRM uW M£ Of '
 container to S to 10 cm HjO (2 to 4 to. HjO).
 and aDow it to stand overnight A deflated
 bag indicate* sleek.
  7.1.1.1 Appararas.
  7.1.1.1.1  Probe. StaJtatessstoaL Pyrex
 glass, or Tenon tubing probe, According to ths
 duct tempeisturs. win tt.4-mni OD Teflon
 tubing of sufficient length to connect to the
 sample bag. Use stainless steel or Teflon
 unions to connect probe and sannsv one*
  7.1.1.1.2  Quick Connects. Male (2) and
 femak (2) of stainless steel construction.
  7.1.1.U  Needle Vahre. To control gas
 flow.        "            •   -
  7.1.1.1.4.  Pump. Leakkss Tefiotw»ated
 diaphragm-type pump or equivalent To
 deliver at least 1 liter/mm.      <   '
  7.1.1.1.5  Charcoal Ao*ofption Tub*. Tube
 rilled witt active ted charcoal, with glass
wool plugs at each end. to adsorb organic
vapors.
  7.1.1.14 nowmeter.OtoSOD-alflow
range: with manufacturer's calibration curve.
  7.1.1.2  Sampling Procedure. To obtain a
 •ample, assemble the cample train a* shown
 ia Figure 1B-B. Leak check both the beg and
 the container. Connect the vacuum line from
 the needle valve to the Teflon sample line

               18-58
                                                                                      from the probe. Place the end of the probe at
                                                                                      the centroid of the stack, and start the pump
                                                                                      'with the needle valve adjusted to yield a flow
                                                                                      of 0.5 liter/minute. After allowing sufficient
                                                                                      time to purge the line neveral times, connect
                                                                                      the vacuum line to the bag, and evacuate
                                                                                      until the rotameter indicates no flow. Then
                                                                                      position the sample and vacuum lines for
                                                                                      sampling, and begin the actual sampling.
                                                                                      keeping the rate proportional to the stack
                                                                                      velocity. As a precaution, 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
                                                                                      temperature, barometric pressure, ambient
                                                                                      temperature, sampling Bow rate and initial
                                                                                      and final sampling time on the data sbeet
                                                                                      shown in Figure 16-10. Protect the Tedlar bag ,
                                                                                      and its container from sunlight When
                                                                                      possible, perform the analysis within 2 hours
                                                                                      of sample collection.      -   .     r
                                                                                        7.1.2  Direct Pump Sampling Procedure.
                                                                                      Flow 7.1.1, except place the pump and needle
                                                                                      vahre between dte probe and the bag. Use a
                                                                                      pomp and needl*. valve constructed of
                                                                                      stainkas stoat or some other material not
                                                                                      affected by the stock gas. Leak check the
                                                                                      system, and then purge with stack gas before
                                                                                      the nonnecMnf to (he previously evacuated
                                                                                      boa,.."-     -;              .
                                                                                        7.U  Explosion Risk Area Bag Sampling
                                                                                      Procedure. Fouow 7.14 except replace the
                                                                                      pump witt another evacuated can (see Figure
                                                                                      l»-»a). Use mis method whenever there I* a
                                                  probes, or other flame producing
  7X4  Other Modified Bag Sampling
Procedures. In the event that condensation is
observed in the beg while collecting th*
sample and a direct interface system cannot
be need beat the bag during collection, and
maintain tt at a snHabry elevated temperature
during aO subsequent operations. (Note: Take
care to leak check the system prior to the
d&otion* so as not to create a potentially
explosive atmosphere.) As an alternative,
collect the sample gee, and simultaneously
dilute it in the Tedlar bag.
  In the first'procedure, heat the box
containing the sample bag to the source
temperature, 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 en insulating blanket to the
analytical area, keep the box heated to
           nrore until analysis. Be sure
                                                                                      that the method of heating Jhe box and the
                                                                                      control for the heating circuit are compatible
                                                                                      with the safety restrictions required in each
                                                                                       To use the second procedure, prefill the
                                                                                     Tedlar bag win a known quantity of inert
                                                                                     gas. Meter the inert gas-into the bag
                                                                                     according to the procedure for the
                                                                                     preparation of gas concentration standard* of
                                                                                     volatile liquid-materials (Section &2^2). but .
                                                                                     eliminate the midget impinger 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, or

-------
 48348     Federal  Register  /  Vol.  48. \;o. 202 / Tuesday.  October 18. 1983  /  Rules and  Regulations
 Teflon positive displacement pump. Verify
 the dilution factors periodically throujyi
 dilution and analysis of gases of known
 concentration.
   7.1.5  Analysis of Bag Samples. Connect
 the needle valve, pump, charcoal tube, and
 flowmeter to draw gai sample* through the
 gas sampling valve. Flush the sample loop
 with gas from one of the three Tedlar bags
 containing a calibration mixture,  and analyze
 the sample. Obtain at least two
 chromatograms for the sample. The results
 are acceptable when the peak areas from two
 consecutive injections agree to within 5
 percent of their average. If they do not agree.
 run additional samples until consistent area
 data are obtained If this agreement is not
 obtained, correct the instrument technique
 problems before proceeding, If the results are
 acceptable, analyze the other two calibration
 gas mixtures ih the same manner. Prepare the
 calibration curve by using the least squares
 method.
   Analyze the two field audit samples as
 described In Section 6.5 by connecting each
 Tedlar bag containing an audit gas mixture to
 the •sampling valve. Calculate the  results:
 record and report the data to the audit
 supervrsoE ff the results are acceptable.
 proceed vrtth the analyvis of the source
 samples.
  Analyze the source gas samples by
 connecting each bag to the sampling valve
 with a piece ofTeflon tubing identified with
 that bag. Follow the restrictions on replicate
 samples specified for the calibration gases.
 Record the data. Analyze the other two bag
 sample* of source gas in the same manner.
 After afi three bag samples have been
 analyzed, repeat the analysis of the
 calibration gas mixture*. Use (he average of
 the two calibration curves -to determine the
 respective sample concentrations. If tin two
 calibration curvet/differ-by more than 5
 percent from their Ben vahw. then -report
 the final ncalts by both ceBbratioa curves.
  7.1.6 Determination of Bag Water Vapor
 Content Meaauw the ambient temperature
 and barometric pressure near the bag. Prom «
water sarnration vapor pressure table,
 determine and record the water vapor
content of the bag as « decimal figure.
 (Assume the relative humidity to be 100
 percent wiles* a leaser vahw is known.)
  Use the field analytical data «heet as
 shown to Figure 18-11. The sheet has been
 designed tolabulate infonsatioe from the bag
 collection, direct interface, and dilute*
 interface systems; as a result, not all of the
 requested information will apply to any
 single method. Note the data that do not
 apply with the notation "N.A." Summarize
 the analysis.       ~~
  72  Direct Interface Sampling and
 Analysis Procedure. The direct interface
 procedure can be used provided that  the
 moisture-content of the gms 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 i» not a
 problem. Adhere to all safety requirements
 with this method.
  7.2.1  Apparatus.
  7.2.1.1   Probe. Constructed of stainless
 steel. Pj rex glass, or Teflon tubing as
 required by duct temperature. 6.4-mm OD.
 enlarged at dncl end to contain glass wool
 plug. If necessary, heat the probe with
 heating tape or a special heating unit capable
 of maintaining duct temperature.
  7.2.1.2  Sample Lines. 6.4-nun 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
 instrument and to pump unit used to
 withdraw source gas. Use a quick connect or
 equivalent on the cylinder or bag containing
 calibration gas to allow connection of the
 calibration gat to the gas sampling valve.
  7.2.1.4   Thermocouple Readout Device.
 Potentiometer or digital thermometer, to
 measure source temperature and probe
 temperature.
  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 GC instrument.
  7.2.1.6   Needle Valve To control gas
 sampling rate from the source
  7.2.1.7   Pump. TjteHrea Teflon-coated
 diaphragm-type pump or equivalent capable
 of at least 1 Qter/nnmite
  7.2.1.8  Flowmeter. Of suitable range to
measure sampling rate.
  73,13  Charcoal Adsorber. To •Hamh
organic vapor collected from the source to
prevent exposure of pacsonnel to source gas.
  7.2J.10  GM Cylinders, Carder gu
(helium or nitrogen), aad oxygen and
hydrogen for a Ham» ionoalioa Am*m**nr (FID)
if one is used.
  7.2.1.11  Gas Chromatograpk  Capable of
being moved into the field, with detector,
heated gas sampling valve, column required
to complete separation of dewed '
components, and option Sat temperature
programming.
  7.2.L12  Recorder/lnlegretor. To record
results.           •                .    '  ~
  7^2 Procedure. To obtain a sample
assemble the  sampling system aj shown in
Figure 18-12, Make sum all connections an
tight Turn on the probe and sample Una
heaters. As the temperature  af the probe and
heated line approaches the source
temperature as indicated on the
thermocouple readout device, control the
heating to maintain a temparatut* of Ote 3'C
above the soatrce temperature. While the
probe and heated fcae ere being heated.
disconnect the aample  line from the gas
sampling. valve, and attach the line from the
calibration gas mixture Flush the sample
loop with calibration gas and analyze a
portion of that gas. Record the results. After
the calibration gas sample has been flushed
into the GC instrument, turn the gas sampling
valve to flush position, then  reconnect the
probe sample line  to the valve. Move the
probe to the sampling position, and draw
source gas into the probe, heated line and
sample loop. After thorough  flushing, analyze
the sample using the same conditions 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 5 percent of their
mean value, analyze additional samples until
two consecutive analyses meet this criteria.
Record the data. After  consistent results are
  obtained, remove the probe from the source
  and analyze a second calibration gas
  mixture. Record this calibration data and the
  other required data on the data sh«et shown
  in Figure 18-11. deleting the dilution gas
  information.
   (Note.—Take care to draw all samples.
  calibration mixtures, and audits through the
  sample loop at the same pressure^
   In addition, analyze the field audit camples
  by connecting the audit sample cylinders to
  the gas sampling valve Use the same
  instrument conditions  as were used for the
  source samples- Record the data, and report
  the results of these analyses to the audit
  supervisor.
   7.3  Dilution interface Sampling and
  Analysis Procedure Source samples that
  contain a high concentration of organic
  materials may require  dilution prior to
  analysis to pi event saturating die GC
  detector. The apparatus required for thi*
  direct interface-procedure is basically the
  same as mat described in the Section 7.2,
  except a tKhitton system is added between
  the heated sample line and the gas sampling
  valve. The apparatus is arranged so that
  either a ion or 10th! dilution of the source,
 gas can be directed to  the chromatograph. A
 pump of larger capacity is also required, and
  this pump must be heated and placed rn the
  system between the sample fine and the
  dilution apparatus.
   7.3.1  Appara ttrs. The equipmen t required
 in addition to that specified for the direct
 interface system is w foflowr
   7.3.1.1  Sample Pomp. Leakless Teflon-
 coated diaphragm-type that can withstand
 being heated to 120*C and deliver 1.5 liters/
 nurrote.   -
   7.3.1.2  Dilution Pomps. Two Model A-150
 Komhyr Teflon positive displacement type
 delivering ISO cc/mmnte. or equivalent. As
 an option, calibrated flowmeters can be used
 in conjunction with Teflon-coated diaphragm
 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 measurement
 of diluent gas, expected delivery flow rate to
 be 1,350 ccymia.
   7.3.1.5  Diluent Gas with Cylinders and
 Regulators. Gas can be nitrogen or clean dry
 air, depending on the nature of the source
 gases.
   7.3.1.6  Heated Box. 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 facilitate
 connection of: (l) The heated sample line
 from the probe (2) the  gas sampling valve (3)
 the calibration gas mixlnret, and (4) diluent
 gas lines. A schematic  diagram of the
 components 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 lft-13 is -
 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.
                                                            18-59

-------
           Federal Register / Vol. 48. No. 202 / Tuesday. October IB. 1983 / Rules  and Regulations      48341
in this w»y. the heated box contain* the
control* for the probe beaten, or. if the box i*
placed against the dnct being sampled, it nay
be possible to eliminate the probe heater*. In
either case, a heated TeQon line is used to
connect the heated box to the gaa ""ipH^fl
valve on the chromatograph.
  7.12  Procedure. Assemble the apparatus
by cuuiieitiiig toe heated box* shown in
Figure 19-13. between the heated (ample line
from the probe and the gas sampling valve on
the uuuuatogiauii. Vent the aouice gee from
the gas saei|iliiig valve directly to the
charcoal filter, eliminating the pomp and
luteuieter. Heait the sample piube, ample
tine. and heated box. Insert the probe and
souice tfaennocoBple at the CBDtroid of the
adiaat aO beating aodto to a toaparatere 0 to
           Off QM lOfloQ
                                          for the particular organic(s) to be sampled.
                                          the following Items (or equivalent) are
                                          suggested.
                                            7.4.1.1  Probe (Optional). Borosilicate glau
                                          or stainleaa steel, approximately fi-mm ID,
                                          with a beating system if water condensation
                                          is a problem, and a filter (either nvetack or
                                          out-stack heated to stack teuipetalure) to
                                          remove particuiate matter. In moat instances.
                                          • plug of glass wool is • satisfactory filter.  v
                                            7.4.12  flexible Tubing. To connect probe
                                          to adsorption tabes. Uae a material that
                                          exhibits minimal sample adsorption.
                                            7.4.1 J  Leaklesa Sample Pump. Flow
                                          controlled, constant rate pump, with a set of
                                          limiting (sonic) orifices n> provide pumping
                                          rates from approximately 10 to 100 cc/mm.
                                            7.4.1.4  Bubble-Tab* Rownwtar Volume
                                          accuracy within ± 1 percent to calibrate
                                                   8toovratcb.TbtiMsaBapimgaad
                                          Repeat the analysis of each sample until the
                                          relative deviation of two consecutive
                                          injections does not exceed 5 percent
                                            7.4.3  Standards and Calibration. The   "
                                          standards can be prepared according to the
                                          respective NIOSH method. Use a minimi^ 4
                                          three different standards; select die
                                          concentrations to bracket the expected
                                          average sample concentration. Perform the
                                          calibration before and after each day's
                                          sample analyses. Prepare the calibration
                                          curve by nsing the least squaras method.
                                            7.4.4  Qualtiy Assurance.
                                            7.4.4.1  Determination of Desorption
                                          nttM.iem»y. During the testing program.
                                          determine the daaorptton efficiency in the
                                          expected seflass concentration range for
OfJaHUC OQOjpQOBaiiV VOnfy IM ODOTOtiOaft Of
the dikooa system by analysing a high

throogh either the 104 or 1004 dtetioB
stages, ae appropriate' ff naoaaaanr. vary die
flowafthadOaMtgMtoobtasBi
dfraton ratios.) nnnajhii the ca
of the nUateil Mllhranan sna aaaag the
                                            7.4*ljB AdvOfpClOB IVDM.
                                          •psclftod by NIO8HL >xc potoot poijfga^pW
                                          adsorbent each aa Tanaoc PC or XAM.
                                                            * Aoomla to ft •• ifgi
                                          SOI
                                                        i ••laminations does not
                                           exceed 5 percent Use the average desorpttoa
                                           aBolBBjcjf of BOM two onneacBtrve
                                           daternunebons lor the correction jpedfiad la
                                           Sectton 7X4S. V the •saorption efficiency of
      > factor and ma
prepared IB the laboratory. Recori tfw
initiuant dala OB die data ahsst ahewa •
FSgnre U-U. Hlhe data on aVa afiasad
calibration g*s an sot within 10 aetosat of
nie expadad valves* oatatBlDa wivniar the
rhinMslngisiih or the rlihilisn s»a>aai is m
               titVarifyneGCi
    j a low concentratioa standard (
diverting the gaa into me siBpli hop.
bypasamg PiaoihrtioB ayataax o I
aaalyaea an aot within acceptable batta,
                                                                           /
                                                             OtolOOoe/ndB.to
              •aft flOW TCtal fffllsM Ml
                 atf AaaJyalkRis
                                           Calibrate the
                                                    EHoaaatnlad
                                                              AaaJyalk
                                                                nOowthai
                                                             of the respective tOOSH
                                           tube fiowmeliv bdijiv
                                           •yvtm Catt Iw QpvBl
                                           loop** lor tUti optratioB. ItMiovd tfav
                                                                       If the back*
                                                                  of the total
                                                             bexfam). repeat the
                                                   with a larger aemplint portion.
                                            7A4J AnabfsaiAaJlt hnmsrllstely
                                                                        te the two
                                                • aofardaace wtth Section 7X2. The
                                                                 with the audit
comet tfaedikitian system to provide the"
QOBfOa lilhllJUil ZMlDtaL MUCB tfait OOROCtfOB
wT QUflXlflgl at •Iglv'^OOOalDuOlai
                                                                                             Aanp Leak Checks and Volume
                                                                                                           i both of the**
                                                                                                      after eaaaphng with aB
raoota'vd.
  Once ft
      » ihe atntioa system end CC
operations an satisfactory, proceed win the
analysis of aoaice gaa. BKl*'yi*m"**aig vie sane
dilution settings as used for the standarda.
Repeal the analyses^ until two cooeecuUvs
vejoaa ooBjot vary by Bsore tnan S percent
turn dMfra*Mn vmtee an obtaiaad
  Ibyaal the amlysto of me calfliraUon gaa
mixtuies to verify aovlpment operation.
Awlyxe the two field aadtt aaaplaa uaing
an^ertWdflato system or dfeectiyoBtmect
to vat gM OaxOBBttDf VWVt M lOOjOfrOQ. RoOOTQ
afl data aod report the rente to the audit
t-1  ... I,—— .». •• ••,*rn•• aogBaatadnut
the taster refer to the National bMtitete of
OrrnpationalSairtjr and Health (MOSH)
method for the particular onjanfca to be
sampled. The principal ttterfereat wiU be
water vapor, g water vapor is present at
concentrations above 9 peiueut aflica gel
sKimlo be need te front of the charcoal.
Where more than one compound is present in
the emissions, then develop relative
adeotptlve capacity iafomiaUon.
  7.4.1   Additional Apparahu. to addition to
the equipment hated in the NIOSH method
  UM ft OaBapH pfOPOe ff lOQfllfOQ. 1
 the leagth of flexible tabing bstueao the
 putMie and adaofptlOB tnibaa. Sevan!
 adsorption tvbee can be connected in series,
 if the extra adeorptive capacity is needed.
 Provide the gu aevpie to the aample systaei
 at a preaaara siifBriiint lor the UmlUiig otlBcie
 to nmcoon aa a aoaJc wilfrfe P^ffr^d tta total
 tine and sample flow rate (or the number of
 pimp atJOHaa). the barometric prasafln. and
 ambient teoaperatore. Obtain a total sample
 voittaae ooaflaBHisQTate wHh the expected
 muoenUaUou(s} of the volatile organicfs)

factors (weight sample per weight adeorpoon
media). Laboratory ta*ts prior to achial
 4Ul JOsm CabOQtat- OCOOiTOlPjg lo uM

 resuha. Use the babble tube flowmeter to
 miaeaie the paasp vobane flow rate with tht
 orifice used m the test sampling, and the
 result ff it has changed by more than S bat"
 leas man 20 percent calculate aa average
 Bow rate for the teat E the flow rate has
 changed by nwre than XO percent recalibras)
 the paaap and repeat the ««»»«pi|"t
  74X1  Calculations All calculations caa
 be aerfomed aocordtog to the respective

                                                                than one organic is
                                          pieaent ID the tiultihfff. **HM* 4t "flop
                                          relative adaorptive capacity information, ff
                                          water vapor is piuent m the samplr at
                                          mucenliaUma above 2 to 3 percent, the
                                          adsorptive capacity may be seveielj reduced.
                                          Operate the gaa chromatograph according to
                                                          instructions. After
                                          establishing optimum conditions, verify and
                                          ducument mese conditioas during afl
                                          operations. Analyze the audit samples (see
                                          Section 7.4.4J), men the emission samples.
NIOSH method. Correct aB sample volu
to steadard conditions. If a sample dilution
system has been ased. multiply th* results bf
the appropriate dimtion ratio. Correct all
results by dividing by the deaorption
efficiency (decimal value). Report results as
ppm by voteme. dry basis.
  7S  Reporting of Results. At the
oomplefion of die field analysis portion of tht
study, ensure that the data sheets shown W
Figure 18-11 have been completed.
Summarize this daU on the dale sheets
shown in Figure 18-15.
8. Bibliogrvphy
  1. American Society for Testing and
Materials. C, Through C, Hydrocarbons in
                                                        18-60

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48350     Federal Register  /  Vol. 48,  No.  202  /  Tuesday, October 18, 1983 / Rules and  Regulations
the Atmosphere by Gat Chromatography.
ASTM D 2820-72. Part 23. Philadelphia. Pa.
23350-956.1973.
  2. Corazon, V. V. Methodology for
Collecting and Analyzing Organic Air
Pottutants. U.S. Environmental Protection
Agency. Publication No. EPA-600/2-79-042:
February 1979.
  3. Dravraeks, A, B. K. Krotoszynaki. ].
Whrineld, A. OThjrmell. and T. Bnrgwald.
Environmental Science and Technology.
^12)1200-1222. 1971.
  4-Eggertsen. F. T.. and E. M. Nelsen. Gas
 Chroma tographic Analysis of Engine Exhaust
 and Atmosphere. Analytical Chemistry. 30(6]:
 10*0-100. 1958.
   S.Feakheller.'W.R-P.J.Mam.IlR
 Harris, and O. L. Hani*. Technical Mannai
 for Process Sampling Strategic* for Organic
 Mattial*. VS. Environmental Protection
 Agency. Research Triangle Park N-C.
 Pubncan'on No. EPA 000/2-78-122. April 1378.
 171 p.
   &. PR. 38 FR 3319-9323. 1874,
   7. FR. 39ER 32857-32800. 1974.
   & IS. 41 FK 23009-23072 and 23076^23090.
 m.   ,
   1& HL 41 fS 43771-«77sV M77.
   11. FMkMte. i. ChianMtDgTvptnr «f
  tariranawnUl Hazards. Volume H. Ebevtor
  Sdaoork Pohusfains Comp«r. New York.
                           F. Maddalone. EPA/ERL-RTP Procedures  ..__
                           Manual: Level 1 Environmental Assessment
                           U.S. Environmental Protection Agency.
                           Research Triangle Park, N.C Publication No.
                           EPA 600/276-16Qa. June 1976. 130 p.
                             13. Harris. J. C, M. J. Hayes. P. L. Levins.
                           and D. B. Lindsay. EPA/IERL4CTP
                           Procedures for Level 2 Sampling and
                           Analysis of Organic Material*. LLS.
                           Environmental Protection Agency. Research
                           Triangle Park. N.C Publication No. EPA fiOO/
                           7-79-031 February 1979. 154 p.
                             14. Harris, W. E., R W. Habgood.
                           Programmed Temperature Gas
                           Chromaiography. John Wiley Ji Sons, Inc.
                           New York Ifl66.
                             IS. Intersooety Committee. Methods of Air
                           Sampling and Analyst*. AmiTi""'*>n"'*"t"1
 Protection Agency. Research Triangle Park,
 N-C Publication No. EPA BOO/2-7C-2CL Jury
 1976.71 p.
   22. Tentative Method for Continaons
 Analysis of Total Hydrocarbons in the
 Atmosphere, tetersticiety Committee,
 American Public Health Association.
 Washington, D.C. 1972. p. 1B4-188.
   23. Zwerg. G, CRC Handbook of
 Chromatogranhy. Volumes I and U. Shenns,
 Joseph (ed^. CRC Press. Cleveland. 1972.
                                                             18-61

-------
OO
I
I.  Naaw of fonpany
    Mdross

    Contoctl
                                                       Otto
                                                                       ttl.
                                                       • WwW^T
         •rocoit to bo toayl od.
         Duet or vont to bo iwplod.
     II. "recoil ditcHptlon
         Raw Mtorlol
         Produeto
         Oporitlng cyclo        /
              Chocki  Bitch «.______. CoBtlnuow
              TiBfng of bitch or ejrolo  .•
              lilt  tfiO tO If»t      •
                  Flgurt 11*1.  PrtllHlnary ourvoy tfato shoot.
lwa>11*f fit*
Duct ohopo sad slto


(jnttrtt-? _1»tt««»

fit* af aceots am
MaiaHt , , r
1. Proportlos of git stroM
Tofltwroturt 	 % ,_^_
V.loHty ,
ftatfe proisurt Iftchos
Notsturo OMtont •
Partlculito contont r ^ •_
ft, ,|
2 «
eft: f
2 I
Hydrocarbon coac«MnU
x ^






m
Inchts 5-
laenaa , dllMtOT __,
<«»»• 	 	 	 ...diamatar ff
"8-
ft
tablont tamp. *F <
S
•f , Data aourco __,... 	 r n , "3.
]_,' Data leurea ^ 	 P
l^O, Data aauret . 	 u. ^
	 Jf, Data lourca ._„ ........ "^
. Data aaurei 	 ft
HydroMrbons ^ 	 ' PP» ^
O
______ o
i

p
. w" -*
— 	 '^JU ( |
	 , PP» ^
	 "*» 8?
to
fliurt IbVI (omtlnuod). Pro11«1n«ry survey data shaat. |
, \

-------
00
en
OJ
    C.  Stapling
        Location to sot tip iC
        Sptclal hazards to »• consfdorttf
        Powtr avallabla at duct _
        Powar avallablt for 6C 	
        Plant s«faty r'aqulramantft
        Vihlclt traffic ruin
        Plant tntry taqulramants
        StcuHty a gratmnts
        Potantlal yroblams
D.  S1ta diagrams.  (Attach additional  fthttts If rtqulnd).

   Flgura 18-1 (continuad).  PrtHorlna'ry survay data shaft.
                                                                    Ce«»on«nt« to  b« •n>lvt«d
                                                                                                         eone«ntr«tion
                                                                     fuggtatad  chromatographle  column
                                                                                                                         nun Hg
                                                                                                                _»C/min
                                                                                                                 •C
Caluan flow rat*     ml/Bin   Road proasura.
Column to»ptratur«»
      Isothtnnal 	    *C
      Prograamtd from       *C to      *C at —
Injection port/aanpl*  loop tomporaturo      ,
Dotoctor tamptraturo         *C
Dttoctor flow ratcai Bydrogtn      ml/mln.
                                hoad proaiuro	  mm Hg
                    Air/Oxygon      al/aln,            /
               -   .              h«ad proaturo      mm Hg
Chart ap««d   ••         incht§/minut«
Compound data*
      Compound     Rotantion timo     Attenuation
                                                                       Figure 11-2.  Chronatographic conditions data sheet.

-------
CX)
 I
cr>
          tlquld
                            Curr* 0«t« -
                             OoUMt«« !• •
         Mf
Kixtura  Nixtura
                                                                      ta»
    •it* ef T*dUr bat  (ilt«r»)
    Dilution f«i  (B«M)
    vol. •( dilation f«s (llMn
    Component  (naaa)
    VoluM of  eoapontnt (•!)
    Av«r««o Mttr tup. (*C)
    Av«r««« votor yroitoro  U»)
    AtHotphario oroiittro (n«)
           of liquid
                                                                  fethod:   fcbblo a»ttr_
                                                                  MotoMtor construction
                          SplroMttr
                                                                                                                 W«t tttt mter
Uboratory taaptraturt (T obi.)
Uboratory trtstttr* (P obi.)
                                                                                                     InHg
                                                                              iwHg
I
                                                                                                       '              Flow ritt  b
                                                                  1.  .  Mo**tUr rtidlno TIM  («1n)  j*i »o1uMB  jltb condUlont)
•ampla loop voluno  (•!)
lanpla loop tonp.  (»C)
Carriar taa flow rata  (•1/aia)
Column tawparaturo
     initial CO
     program rata  (•C/aUn)
     final CO
Znjaetion timo (24  dr. baaia)
Diatanea to paak  (OB)       <
Chart apaad  (cm/tain)
Ratantion tino (mia)
Cclculatad eoneantration  (ppa)
Attanuator Batting
•aak haieht (m)
Paak araa  (BB*)
Araa •  attanuation /
•lot paak araa x attanuation ataUat aoneantratioa to obtain
ctllbratlan turn.  '
                                                                       •  Vol. of gu My M Muurtd 1« •WIHttri, llttn or euble fitt.
                                                                       b  Convtrt to ltandtr4  eondltlom (2Q0 C and 760 m Hg),
                                                              PVT °tV
                                                              t obi. x zu
                                                                                                                   1/2
                                                                                                                     ntt (Sfp conditions)
             riaurt W-l.- Cilbratlon turn <•*• "J"* r <"Jaet1o«
                      of veUtlla Mapla <«ta TNUf aa|.
                                                                    Mot uttr rottflng .gtlwt flo- «tt (•«) ••* dr« loiooth curvt.

                                                                                     1M.   RoUMttr calibration data shtat.
                                                                                                                                             o^
                                                                                                                                             £
                                                                                                                                             2
                                                                                                                                             p
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                                                                       i5
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48354      Federal Register / Vol. 48, No. 202 / Tuesday, October 18,1983 / Rules and Regulations
COMPONENT
   CAS
 CYLINDER
   DIUIENT
    GAS
  CYLINDER
\
                           CALIBRATED ROTAMETERS
                             WITH ROW CONTROL
                                   VALVES
                      •i" CONNECTOR
                                                                   TEDLARBAG
               Figure W-5.  Single-stage calibration gas dllrtlon system
                                     HIGH
                                 CONCENTRATION
                                    WASTE
                                      X-0—NEEDLE VALVES
            ROTAMtTERS-
                                       LOW
                                  •CONCENTRATION
                                       GAS
                                           PRESSURE
                                           REGULATOR
                             DILUENT AIR
                  DILUENT AIR
     PURE SUBSTANCE OR
 PURESUBSTANCE/NZ MIXTURE
                     Figure 18-6.  Two-stage dilution apparatus.

                                              18-65

-------
00
I
CTI
cr>
1.  lien concentration

          Component __

          Diluent fee .
                                aixture
                                        Concentration
                                                    Bate
                                      Mixture 1  Mixture >  fff»ture I
9.  Dilution and analysis  eta

          ttaae I

Component gas-rotimetcr retdiaf
Diluent gas-rotametor rosdinf
Ambient temp. (*C)
tunoMto'r reading, inches ItO
riow rate component gas (ml/min)
flow rate diluent gas (ml/tin)

          ttaqe 8
Component gas-rotametor reading
Diluent gaa-rotaiMtor reading
riow rate coetponent gas (sU/aia)
Flow rate diluent gas (ml/min)
Calculated concentration (ppei)

       /   Analysis
•ample loop-volua*  (al)
•ample loop temp.  (*C)
Carrier gas flow rate (al/ala)
Column temperature
     initial  (*C)
     program  rate  (•C/mia)
     final  (*C)
Injection time  (24>hr•
Distance to peak  (iachos)
Chart  speed  (inch/feia)
Retention tim*  (aia)
Attenuator factor
Peak height  (••)
Peak area  (mm*)
Area « Attenuation  factor  (am1)
Plot peak area •  attenuator  factor agaiaat concentration to
3. , low iDMeatratio* staaiaH
          AWMI oooeentretioa (pp«)
          KetMtioa tlM (iOa)

          Zajootioa tia« (24-toer
          AtMaMtiw faetor

          Peak aoifhfe (•)

          Peak ana («O                .
          Peak ana • atteaoatioa (a*1)  _
          Calovlatoi eonceatration  he«t -
                     Flevre'IV-7.  CallkntleM evrv* detf sheet •
                              dlletlea MtMd.
                                                                        58
                                                                        s
                                                                        I

                                                                       I
                                                                        ID
                                                                        cr.
                                                                        I

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48356	Federal Register /"VoL 48. Na. 202 / Toiasday, October 18,1983 / Rules and Regulations
                               BOILING •*
                                WATER
                                 BATH
                                                  SYRINGE
                                                   SEPTUM
                                                    . MIDGET
                                                     IMPINGER
                                          HOTPLATE
                       NITROGEN
                       CYLINDER
                                                  CAPACITY
                                                  50 LITERS
                   Figure 18-8.  Apparatus for preparation of liquid materials.
        STACK
        VM1
  nun   fl
MASS WOOL) II
   10101
.SAMTICUNE
                      RIGID UAKPROOF CONTAINOt
               Figure 18-9.  Integrated bag sanpllng train.

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            Federal Register / Vol. 48. No. 202 / Tuesday. October 18. 1983 / Rules and Regulations       48357


                                           WC Tubing
5' Trflcn Tublita


   Pinch Clwe)
                  GrtMKt

      Air Tlett Steel
                                                /
Directional
NeHIt Vtlvt
                                                                            Ivtcmttt Stetl
                            Figure 18-9*.  Explosion risk gas soiling wthod.
flwt
touro
          rttefoor.)
Stwtttai
        Flfur* 18-10.  Field svpU «iti shMt • TtdUr
                              Mtaod.
                                                18-68

-------
     Location
                                                 Bate
CTi
>O
1.  General  information
          Source temperature (*C)
          Probe temperature  (*C)
          Ambient  temperature (»C)
          Atmospheric pressure  (am)
          Source pressure  CBg)
          Absolute source pressure  (HI)
          Sunpling rate (liter/bin)
          Sample loop voluM (al)
          Staple loop temperature  (*C)
          Columnar temperaturei
               Initial  (*c)/tiae  lain)
               Program  riti  {«C/min»
               final (*C)/tlM  (alnV
          Carrier oas flow rate  (ml/min)
          Detector temperature '('O
          Injection time (24-hour bull)
          Chart ipeed (mm/ain)

          Dilution oas  flow  rate  (al/aia)
          Dilution Cas  used  (syabol)
          Dilution ratio
                     Figure 18-11.  Field am lysis dita shetU.
Ti«ld Analysie Oat*  - Calibration Oaa
Run He.               Tiae	
Components   Area    Attenuation   A x A Factor   Cone, (ppm)
                                                                                       Mo.
                     Tiae    ...
                                                                                   Components    Area    Attenuation   A * A factor   Cone, (ppm)
                                                                                                         Tiae
Run no.   . „
Components   Area   Attenuation   A x A.fraetor,   Cone,  (ppm)
                                                                                             H
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           Federal Register / Vol. 48. No. 202 / Tuesday, October 18,1983 / Rules and Regulations        48359
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                                               18-70

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48360      Federal  Register /  Vol.  48.  No.  202  /  Tuesday.  October  18.  1983  /  Rules  and  Regulations
Gaseous Organic Sampling and Analysis
Check List
(Respond with initials or number as
appropriate)
                                                                   Source
                                                                  Mmple 1
                                  Source
                                  sample 2
                                     Source
                                    sample 3
                                         Date
                                                    Source
                                                     preuurc
                                                     (mm Hg)	..
                                                    Sampling rate
t Prmrvey data:
      A. Grab sample collected	
      B. Crab aample analyzed for com-
        poaiuon-.       	
             Method CC		
                   CC/MS	
                   Other	
      C. GC-FTD analyaii performed.......
I Uboratory calibration data:
      A. Calibration curvet prepared	
             Number of component ....
             Number   of  concentra-
              boni/cooipooeot (J re-
              quired)	
      B. Audit tanptes (optional):
             AaaJytia completed	
             Verified  tor  coocentra-
                                   D .	
                                   a
                                   a
                                   a
                                   D	

                                   o-......
                                   D
a
a
a
                                            a

                                            a
             OK  obtained  for  field
               work.
 .1 tiamHin procedurea:
       A, Method:
             Ovect oMerface	
             Dttaoon iMerfac*	
       a Mamriir of aaamp*ea collected —
 iFWdanaryw
       A. Tout hydrocarbon  aoalyoa
         P-fa
       B. CaU
                      r prepared —
             Number of uianpnnantj..
                      of
                                   a
                                   n
                                   a
                                   a.
                                   a ....
                                   a....
                                   a
a
a
o
               raqulrad)-
                                            a

                                            a
Sample loop
  volume (ml) ....
Sample loop
  tempera lure
  CO	
Sample
  collection
  time (24-hr
  beau)—__....
Column
  temperature:
    Initial |'C)...
    Pioej am
     rate
     CC/min)..
    Final cq.._
Carrier fa*
  flow rate
  (ml/nun)	_
Detector
  tempera tun
  TO.
Chart tpecd
  (cm/nun)—

Dilutioa (a*
  flow rat*
  (ml/min)-
Diluent fat
  uaed
  (tymbol)	
Dilutioa rattg_
                                                 Ptrfonned by (tignature):	
Fignre 1H*- Sampling and analysis check.
CeiiOBi Organk Sampling and Analysis
                                                  Date-.—
                                                  Figure 1&-14. Sampling and analysis sheet.
 ««nt-
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                                         Source
      TO
      •be

      ro
      •Oil

      rof
                                                                     13-71

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40 CFR "art 60, Appendix A
Final ,  promulgated
                 METHOD 21.   DETERMINATION  OF  VOLATILE
                         ORGANIC  COMPOUND LEAKS
   1.  Applicability and Principle
        1.1  Applicability.   This method applies  to  the  determination of
   volatile organic compound  (VOC)  leaks from  process  equipment.  These
   sources include, but are  not  limited  to, valves,  flanges  and  other
   connections,  pumps and compressors,  pressure  relief  devices,  process
   drains, open-ended valves,  pump  and  compressor seal  system degassing
   vents, accumulator vessel  vents,  agitator seals,  and  access door
   seals.
        1.2  Principle.  A portable instrument is used  to detect VOC
   leaks fron  individual sources.  The  instrument detector type  is  not
   specified,  but  it must meet the  specifications and  performance criteria
   contained in  Section 3.   A leak  definition  concentration  based on a
   reference compound is specified  in  each  applicable  regulation.  This
   procedure is  intended to  locate  and  classify  leaks  only,  and  is  not to
   be  used as  a  ci>-ect measure of mass  emission  rates  from individual
   sources.
   2.  Definitions
        2.1  Leak  Definition Concentration.  The local  VOC concentration  at
   the surface cf  e leak source that indicates that a  VOC emission  (leak)
                                  21-1

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is present.  The leak definition is an instrument meter reading based
on a reference compound.
     2.2  Reference Compound.  The VOC species selected as an instrument
calibration basis for specification of the leak definition concentration.
(For example:  If a leak definition concentration is 10,000 ppmv as
methane, then any source emission that results in a local concentration
that yields a meter reading of 10,000 on an instrument calibrated with
methane would be classified as a leak.  In this example,  the leak
definition is 10,000 ppmv, and the reference compound  is  methane.)
     2.3  Calibration Gas.  The VOC compound used to adjust the instrument
meter reading to a  known value.  The  calibration gas is usually the
reference compound  at a concentration approximately equal to the leak
definition concentration.
     2.4   No Detectable Emission.  The local VOC concentration at the
surface of a leak source that indicates that a VOC emission (leak) is
not present.  Since background VOC concentrations may exist, and to
account for instrument  drift and imperfect reproducibility, a difference
between the source surface concentration and the local ambient con-
centration is determined.  A difference based on meter readings of
less than a concentration corresponding to the minimum readability
specification indicates that a VOC emission (leak) is  not present.
 (For example, if the leak definition  in a regulation is 10,000 ppmv,
then the allowable increase in surface concentration versus local
ambient concentration would be 500 ppmv based on the instrument meter
 readings.)
                                21-2

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     2.5  Response Factor.  The ratio of the known concentration of  a
VOC compound to the observed meter reading when measured using an
instrument calibrated with the reference compound specified in the
application regulation.
     2.6  Calibration Precision.  The degree of agreement between
measurements of the same known value, expressed as the relative percentage
of the average difference between the meter readings and the known
concentration to the known concentration.
     2.7  Response Time.  The time interval from a step change in VOC
concentration at the input of the sampling system to the time at which
90 percent of the corresponding final value is  reached as displayed on
the instrument readout meter.
3.   Apparatus
     3.1  Monitoring Instrument.
     3.1.1  Specifications.
     a.  The VOC  instrument  detector shall  respond  to  the  compounds
being processed.  Detector  types  which  may  meet this  requirenent include,
but are not limited  to,  catalytic oxidation,  flame  ionization,  infrared
absorption, and photoionization.
     b.  The  instrument  shall  be  capable of measuring  the  leak  definition
concentration  specified  in  the  regulation.
     c.  The  scale  of  the instrument meter shall be readable to ±5
percent of  the specified leak definition concentration.
      d.  The  instrument shall be equipped with a punp so that a continuous
sample  is  provided  to  the detector.   The nomine! sample flow rate shall
 be 1/2  to  2 liters  per minute.
                                21-3

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     e.  The instrument shall be intrinsically safe for operation in
explosive atmospheres as defined by the applicable U.S.A. standards
(e.g., National  Electrical Code by the National Fire Prevention Association)
     3.1.2  Performance Criteria.
     a.  The instrument response factors for the individual compounds
to be measured must be less than 10.
     b.  The instrument response time must be equal to or less than 30
seconds.  The response time must be determined for the instrument
configuration to be used during testing.
     c.  The calibration precision must be equal to or less than 10
percent of the calibration gas value.
     d.  The evaluation procedure for each parameter is given in
Section 4.4.
     3.1.3  Performance Evaluation Requirements.
     a.  A response factor must be determined for each compound that
is to be measured, either by testing or from reference sources.  The
response factor tests are required before placing the analyzer into
service, but do not have to be repeated at subsequent intervals.
     b.  The calibration precision test must be completed prior to
placing the analyzer into service, and at subsequent 3-month intervals
or at the next use whichever is later.
     c.  The response time test is required prior to placing the
instrument into service.  If a modification to the sample pumping
system or flow configuration is made that would change the response
time, a new test is required prior to further use.
                               21-4

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     3.2  Calibration Gases.   The monitoring instrument is calibrated
in terns of parts per million by volume (ppmv) of the reference compound
specified in the applicable regulation.  The calibration gases required
for monitoring and instrument performance evaluation are a zero gas
(air, less than 10 ppmv VOC)  and a calibration gas in air mixture
approximately equal to the leak definition specified in the regulation.
If cylinder calibration gas mixtures are used, they must be analyzed
and certified by the manufacturer to be within +2 percent accuracy,
and a shelf life must be specified.  Cylinder standards must be either
reanalyzed or replaced at the end of the specified shelf life.  Alter-
nately, calibration gases may be prepared by  the user  according to any
accepted gaseous standards preparation procedure that  will yield a
mixture accurate to within +2 percent.   Prepared standards must be
replaced each day  of use unless  it can be demonstrated that degradation
does not occur during  storage.
     Calibrations  may  be performed using a  compound  other than the
reference  compound  if  a conversion factor  is  determined for that
alternative  compound  so that the resulting  meter readings during
source  surveys  can be  converted  to  reference  compound  results.
4.   Procedures
      4.1   Dretest Preparations.   Perform the instrument evaluation
procedures given in Section  4.4 if  the evaluation requirements of
Section 3.1.3 have not been  met.
      4.2  Calibration Procedures.   Assemble and start up the VOC
analyzer according to the manufacturer's instructions.  After the
                                21-5

-------
appropriate warmup period and zero or internal calibration procedure,
introduce the calibration gas into the instrument sample probe.
Adjust the instrument meter readout to correspond to the calibration
gas value.  (Note:  If the meter readout cannot be adjusted to the
proper value, a malfunction of the analyzer is indicated and corrective
actions are necessary before use.)
     4.3   Individual Source Surveys.
     4.3.1  Type  I - Leak Definition Based on Concentration.   Place
the probe  inlet at the surface of the component interface where  leakage
could occur.  Move the probe along the interface periphery while
observing  the instrument readout.  If an increased meter reading is
observed,  slowly  sample the interface where leakage  is  indicated until
the maximum meter reading  is obtained.   Leave the  probe inlet  at this
maximum  reading location for approximately  two  times tbe instrument
response  time.  If the maximum observed  meter reading is greater than
the leak  definition  in the applicable regulation,  record and  report
the results as specified in the  regulation  reporting requirements.
Examples  of the application of this  general technique to specific
equipment types are:
      a.   Valves—The most  common source  of  leaks  from valves  is  at the
seal  between  the  stem  and  housing.   Place  the probe at the interface
where the stem exits the  packing-gland  and  sample the stem circumference.
Also,  place  the  probe  at  the  interface  of  the packing gland take-up
flange seat  and  sample the periphery.   In  addition, survey valve
 housings of  multipart  assembly  at the surface of  all interfaces  where
 leaks could  occur.
                                21-6

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     b.  Flanges and Other Connections—For welded flanges, place the
 probe at the outer edge of the flange-gasket interface and sample the
 circumference of the flange.  Sample other types of nonpermanent
 joints (such as threaded connections) with a similar traverse.
     c.  Pumps and Compressors—Conduct a circumferential traverse at
 the outer surface of the pump or compressor shaft and seal interface.
 If the source is a rotating shaft, position the probe inlet within 1 cm
of the shaft-seal  interface for the survey.  If the housing configuration
prevents a complete traverse of the shaft periphery, sample all accessible
portions.  Sample all other joints on the pump or compressor housing
where leakage could occur.
     d.  Pressure Relief Devices--The configuration of most pressure
relief devices prevents sampling at the sealing seat interface.  For
those devices equipped with an enclosed extension, or horn, place the
probe inlet at approximately the center of the exhaust area to the
atmosphere.
     e.  Process Drains--For open drains, place the probe inlet at
approximately the center of the area open to the atmosphere.  For
covered drains,  place the probe at the surface of the cover interface
and conduct a peripheral traverse.
     f.  Open-Ended Lines or Valves--Place the probe inlet at approximately
the center of the opening to the atmosphere.
     g.  Seal System Degassing Vents and Accumulator Vents—Place the
probe inlet at approximately the center of the opening to the atmosphere.
                               21-7

-------
     h.  Access Door Seals—Place the probe inlet at the surface of
the door seal interface and conduct a peripheral traverse.
     4.3.2  Type II - "No Detectable Emission".
     Determine the local ambient concentration around the source by
noving the probe inlet randomly upwind and downwind at a distance of
one to two meters from the source.  If an interference exists with
this determination due to a nearby emission or leak, the local ambient
concentration may be determined at distances closer to the source, but
in no  case shall the distance be less than 25 centimeters.  Then move
the probe inlet to the surface of the source and determine the concentration
described in 4.3.1.  The difference between these concentrations
determines whether there are no detectable emissions.  Record and
report the results as specified by the regulation.
     For those cases where the regulation requires a specific device
installation, or that specified vents be ducted or piped to a control
device, the existence of these conditions shall be visually confirmed.
When the regulation also requires that no detectable emissions exist,
visual observations and sampling surveys are required.  Examples of
this technique are:
     (a)  Pump or Compressor Seals—If applicable, determine the type
of shaft seal.  Perform a survey of the local area ambient VOC concentration
and determine if detectable emissions exist as described above.
     (b)  Seal System Degassing Vents, Accumulator Vessel Vents,
Pressure Relief Devices—If applicable, observe whether or not the
applicable ducting or piping exists.  Also, determine if any sources
                                21-8

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exist in the ducting or piping where emissions could occur prior to
the control device.  If the required ducting or piping exists and
there are no sources where the emissions could be vented to the atmosphere
prior to the control device, then it is presumed that no detectable
emissions are present.  If there are sources in the ducting or piping
where emissions could be vented or sources where leaks could occur,
the sampling surveys described in this  paragraph shall be  used to
determine  if detectable emissions exist.
     4.3.3  Alternative Screening Procedure.   A screening  procedure
based on the formation of  bubbles in a  soap  solution  that  is sprayed
on  a potential  leak  source may be used  for those  sources  that  do  not
have continuously  moving  parts,  that do not  have  surface  temperatures
greater than the boiling  point or less  than  the  freezing  point of the
soap solution,  that do  not have  open  areas to the atmosphere that the
soap solution  cannot bridge,  or  that  do not exhibit evidence of liquid
leakage.   Sources  that have these  conditions present must be surveyed
using  the  instrument techniques  of  4.3.1 or 4.3.2.
      Spray a  soap  solution over  all  potential leak sources.  The soap
 solution nay  be a  commercially available leak detection solution or
 r>ay be prepared using concentrated detergent and water.  A pressure
 sprayer or a squeeze bottle may be used to dispense  the solution.
 Observe the potential leak sites to determine if any bubbles are
 formed.   If no bubbles are observed, the  source  is presumed to have no
 detectable emissions or  leaks,  as applicable.  If  any  bubbles are
 observed, the  instrument  techniques of 4.3.1  or  4.3.2  shall be used to
                                 21-9

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determine if a leak exists, or if the source has detectable emissions,
as applicable.
     4.4  Instrument Evaluation Procedures.  At the beginning of the
instrument performance evaluation test, assemble and start up the
instrument according to the manufacturer's instructions for recommended
warmup period and preliminary adjustments.
     4.4.1  Response Factor.  Calibrate the instrument with the reference
compound as specified in the applicable regulation.  For each organic
species that  is to be measured during individual source surveys,
obtain or prepare a known  standard  in air  at a  concentration of approximately
80 percent  of the applicable leak definition unless  limited by volatility
or explosivity.   In these  cases, prepare a standard  at 90  percent of
the saturation concentration, or 70 percent of  the lower explosive
limit, respectively.  Introduce this mixture to the  analyzer and
record the  observed meter  reading.   Introduce zero air until a stable
reading is  obtained.  Make a total  of three measurements by alternating
between the known mixture  and zero  air.  Calculate the response factor
for each repetition and the average response factor.
     Alternatively, if  response factors have been published for the
compounds of interest for  the instrument or detector type, the  response
factor determination  is not  required,  and  existing  results may  be
referenced.   Examples of  published  response  factors  for  flame  ionization
and catalytic oxidation detectors  are  included  in  Section  5.
      4.4.2   Calibration Precision.   Make  a total  of  three  measurements
by alternately using  zero  gas  and  the  specified calibration gas.
                                21-10

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Record the meter readings.  Calculate the average  algebraic difference
between the meter readings and the known value.  Divide this average
difference by the known calibration value and multiply by 100 to
express the resulting calibration precision as a percentage.
     4.4.3  Response Time.  Introduce zero gas into  the instrument
sample probe.   When the meter reading has stabilized, switch quickly
to the specified calibration gas.  Measure the time  from switching to
when 90 percent of the final stable reading is attained.  Perform this
test sequence three times and record the results.  Calculate the
average response time.
5.  Bjbliography
     5.1  DuBose, D.A., and G.E. Harris.  Response Factors of VOC
Analyzers at a Meter Reading of 10,000 ppmv for Selected Organic
Compounds.  U.S. Environmental Protection Agency,  Research Triangle
Park, N.C.  Publication No. EPA 600/2-81-051.  September 1981.
     5.2  Brown, G.E., et al.  Response Factors of VOC Analyzers
Calibrated with Methane for Selected Organic Compounds.  U.S. Environmental
Protection Agency, Research Triangle Park, N.C.  Publication No. EPA
600/2-81-022.   May 1981.
     5.1  DuBose, D.A., et al.  Response of Portable VOC Analyzers to
Chenical Mixtures.  U.S. Environmental Protection  Agency, Pxesearch
Triangle Park, N.C.  Publication No. EPA 600/2-81-110.  September 1981.
                                21-11

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         Federal Register /  Vol. 48,  No.  161 /  Thursday, August 18. 1983 /  Rules  and Regulations
                                          1.1  Applicability. This method applies to
                                        the determination of volatile organic
                                        compound (VOC) leak* from process
                                        equipment These sources include, but are not
                                        limited to, valves, flanges and other
                                        connections, pump* and compressors,
                                        pressure relief devices, process drains, open-
                                        ended valves, pump and compressor seal
                                        system degassing vents, accumulator vessel
                                        vents, agitator seals, and access door seals.
                                          13  Principle. A portable instrument is
                                        used to detect VOQ leaks from individual
                                        sources. The instrument detector type is not
                                        specified but it must meet the specifications
                                        and performance criteria contained in Section
                                        9. A leak definition concentration based on a
                                        reference compound is specified in each
                                        applicable regulation. This piucethire is
                                        intended to locate and classify leaks only.
                                        and is not to be used as a direct measure of
                                        mass  emission rates from individual sources.
                                          2. Definition*.
                                          2.1  Leak Definition Concentration. The
                                        local  VOC concentration at the surface of a
                                        .leak source that indicates that a VOC
                                        smissiOB (leak) is present Tba leak definition
                                        is an  instrument meter reading baaed on a
                                        reference compound.
                                          Z2 *sfef»nc» Compound The VOC
                                        spades selected as an instrument calibration
                                        basis for specification of the leak definition
                                        concentration. (Far •»••»!«'•• If « leek
                                        definition concentration is lOjOOO ppnv as
                                        nfdw". than any source •mission that
                                        results !• a local concentration that yields a
                                        meter reading of 10400 on an instrument
                                        calibrated with methane would be classified
                                        as a leak, u this example, the leak definition
                                        is 10400 ppmv. and the lefeience compound

                                          13
                    i of Volants Orgasmc
1. Applicability and Principle.
«sed to adjust the instrument meter reading
to a known TaJoe. The calibration gas is
•soaUy the lefereaca compound at a
concentration approximately equal to the
leak definition content! stiun.
  2.4  No Detectable EmiMion. The local
VOC concentration at the surface of a leek
source that indicates that a VOC emission
(leak) is not present Since background VOC
concentrations nay exist and to account for
MsUument drift and imperfect
reprodndbility. a difference between the
source surface concentration and the local
ambient concentration is determined. A
duMrencs based on meter readings of less
thefts concentration correspondmg lO'the
minimum readability fp*rif>*»*kp« indicates
mats VOC emission (leak) is not present
(For example, if the teak definition ma
regulation is 1OOOO ppmv, then the allowable

ambient concentration would be SOD ppmv
based on the instrument meter readings.)
  25  AaapwiM factor. The rate of the
known concentration of a VOC compound to
the observed meter reeding when msaiuied
sang an instrument calibrated with die
reference compound specified in the
application regulation.
  20  Calibration PrecMoa. The degree of
       at between measurements of the
    i known value, Bxpnusd as the relative
percentage of the average difference between
the meter readings and the known
concentration to the known concentration.
                                             2.7  Response Time. The time interval
                                           from a step change in VOC concentration at
                                           the input of the sampling system to the time
                                           at which 90 percent of the corresponding final
                                           value is reached as displayed on the
                                           instrument readout meter.
                                             3. Apparatus.
                                             3.1  Monitoring Instrument.
                                             3.1.1   Specifications.
                                             a. The VOC instrument detector shall
                                           respond to the compounds being processed.
                                           Detector types which may meet this
                                           requirement include, but- are not limited to,
                                           catalytic oxidation, fiante ionization. infrared
                                           absorption, and pbotokmization.
                                             b. The instrument shall be capable of   ,
                                           measuring the teak definition concentration
                                           specified in the regulation.
                                             c. The scale of the instrument meter shall
                                           be readable to 5 percent of the specified leak
                                           definition concentration.
                                             d. The instrument shall be equipped with a
                                           pomp so that a continuous sample is provided
                                           to the detector. The nominal sample flow rate
                                           shall be Vt to 3 Uters per minute.
                                             e. The instrument shell be intrinsically safe
                                           for operation in explosive atmospheres as
                                           defined by the applicable USA. standards
                                           (e*. National Electrical Code by the National
                                           Fire Prevention Association).
                                             3.1 J  Performance Criteria.
                                             a. The instiumeut response factors for the
                                           mdrvidal compounds to be measured must be
                                           less man 10.
                                             b. The instrument response tune must be
                                           equal to or toes than 30 seconds. The
                                           response time must be determined for the
                                           instrument configuration to be used during
                                           lTT"'^fl.
                                             c.Thei
  c. The calibration precision most be equal
to or less than 10 percent of the calibration
gttvatoe.
  d. The evafostion procedure for each
parameter is given in Section 4.4.
  3.13 Performance Evaluation
Requirement*.
  a. A response factor must be determined
for each compound that is to be measured.
either by testing or from reference sources.
The response factor tests are required before
piecing the analyzer into service, bat do not
have to be repeated as subsequent intervals.
  b. The calibration precision test must be
completed prior to placing the analyzer into
service, end at subsequent 3-month intervals
or at the next use whichever is later.
  c. The response time test is required prior
to placing the instrument into service. If s
modification to the sample pumping system
or flow configuration is made that would
change the response time, a new test is
required prior to further use.
  3j  Calibration Coses. The monitoring
instrument is calibrated in terms of parts per
million by volume (ppmv) of the reference
compound specified in the applicable
regulation. The calibration gases required for
monitoring and instrument performance
evaluation era a sera gas (air, less than 10
ppmv VOC) and a calibration gas in air
mixture approximately equal to the leak
definition specified in the regulation. If
cylinder calibration as mixture are used, they
mast be analyzed and certified by the
manufacturer to be within ±2 percent
                                                           21-12

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           Federal ftegister  / Vol.  48. No. 161 / Thursday,  Augnst 18. 1983 /  Rules and Regulations
accuracy, aad a shelf life moat be specified.
Cylinder standard* mat be either waaajyxed
or replaced ai the «nd of the specified shelf
fife. Alternately, calihratiaa gates n«y a*
{prepared by the oser according to any
accepted gaseous standard* preparation
procedure that will yield a mixture accurate
to within ±2 peacest Pwparad standards
•utl be replaced each day of BM OBasff ft
can be demonstrated that degradation does
not occur during storage.
  Calibrations may be performed using a
compound other than the reference
compound if a conversion factor is
determined for that alternative compound so
that the resulting meter readings during
source surveys can be converted to reference
compound results.
  4, Procedures.
  4,1  Pretest Preparations. Perform the
instrument evaluation procedures given in
Section 4.4 if the evaluation requirements of
Section 3.1.3 have not been met.
  43  Calibration Procedures. Assemble and
tUrt up the VOC analyzer according to the
Manufacturer's instructions. After the
appropriate wannup period and zero internal
calibration procedure, introduce the
calibration gaa into the instrument sample
probe. Adjust the instrument meter readout to
correspond to  the calibration gas value.
  Nots^-If the meter readout cannot be
adjusted to the proper value, a malfunction of
tba analyzer is indicated and corrective
actions are necessary before use.
  4j  Individual Source Surveys.
  44.1 Type I—Leak Definition Based on
Concentration. Place the probe inlet at the
Bvface of the component interface where
lailragr could occur. Move the probe along
to interface periphery while observing the
taatrament readout If an increased meter
iailing is observed, slowly sample the
taktrface where leakage is indicated until the
SHximum meter reading is obtained. Leave
the probe inlet at this maximum reading
location for approximately two times the
instrument response time. If the maximum
obauiuJ meter reading is greater than the
hak definition in the applicable regulation.
racord and report the results as specified in
las regulation reporting requirements.
Examples of the application of this general
technique to specific equipment types are:
  a. Valves—The most common source of
Inks from valves is at the seal between the
Stan and housing. Place the probe at the
terface where the stem exists the packing
aland and sample the stem circumference.
Also, place the probe at the interface of the
lacking gland take-up flange seat and sample
AN periphery. In addition, survey valve
housings of multipart assembly at the surface
of all interfaces where leak could occur.
  b. Flanges and Other Connections—For
wtkled flanges, place the probe at the outer
•Oft of the flange-gasket interface and
ample the circumference of the flange.
Suople other types of nonpennanent joints
(•Mb, as threaded connections) with a similar
  c. Pumps and Compressors—Conduct a
 cfacumferential traverse at the outer surface
 of the pump or compressor shaft and seal
 interface. If the source is a rotating shaft.
 position the probe inlet within 1 cm of the
 shaft-seal interface for the survey, H, the
 housing configuration prevents a complete/
 traverse of the shaft periphery. """pfo aJJ
 accessible penlkms. Sample attother joints
 on the pump or compressor hawing where
 leakage eo«)d aeon.
   i. ftesgum. ReRef Pgvfces—The
 configuration of moat piesure refief devices
 prevents sampling at the aeo&ng seat
 interface. For those devices equipped wih an
 enclosed extension, or horn, place the probe
 inlet at approximately the center of the
 exhaust area to the atmosphere.
   e. Process Drains—For open drains, place
 the probe inlet at approximately the center of
 the area open to the atmosphere. For covered
 drains, place the probe at the surface of the
 cover interface and conduct a peripheral
 traverse.
   f. Open-Ended Lines or Valves—Place the
 probe inlet at approximately the center of the
 opening to the atmosphere.
   g. Seal System Degassing Vents and
 Accumulator Vents—Place the probe inlet at
 approximately the center of the opening to
 the atmosphere.
   h. Access Door Seals—Place the probe  inlet
 at the surface of the door seal interface and
 conduct a peripheral traverse.
   4.32  Type II—"No Detectable Emission ".
   Determine the local ambient concentration
 around the source by moving the probe inlet
 randomly upwind and downwind at a
 distance of one to two meters from the
 source. If an interference exists with this
 determination due to a nearby emission or
 leak, the local ambient concentration may be
 determined at distances closer to the source.
 but in no case shall the distance be less than
 25 centimeters. Then move the probe inlet to
 the surface of the source and determine the
 concentration described in 4 J.I. The
, difference between these concentrations
 determines whether there are no detectable
 emissions. Record and report the results as
 specified by the regulation.
    For those cases where the regulation
 requires a specific device installation, or that
 specified vents be ducted or piped to a
 control device, the existence of these
 conditions shall be visually confirmed. When
 the regulation also requires that no
 detectable emissions exist visual     —
 observations and sampling surveys are
 required. Examples of this technique are:
    (a) Pump or Compressor Seals—If
 applicable, determine the type of shaft seal
 Preform a survey of the local area ambient
 VOC concentration and determine if
 detectable emissions exist as described
 above.
    (b) Seal System Degassing Vents,
 Accumulator Vessel Vents, Pressure Relief
 Devices—If applicable, observe whether or
 not the applicable ducting or piping exists.
 Also, determine if any sources exist in the
 ducting or piping where emissions could
 occur prior to the control device. If the
 required ducting or piping exists and there
 are no sources where the emissions could be
 vented to the atmosphere prior to the control
 device, then it is presumed that no detectable
 emissions are present If there  are sources in
 the ducting or piping where emissions could
 be vented or sources where leaks could
 occur, the sampling surveys described nythis
paragraph shall be used to detenaan* B
delectable, amissioi
        Alternative Srrrniiaf Pfacwaare. A
screening: pcocedui*; based OB tbat iomdni
of bubble* M> • s*«p svtuCiat tfeai hi censed
on a patea&at aeaki
the** soacces that do ant hi
moving parts, that do not haveswEsee
temperatiues greiiagi than the boiSiig point or
less thm the nosering-pon* of the soap
solution, that do not have open areas to the
atmosphere that the soap solution cannot
bridge, or that do not exhibit evidence of
liquid leakage. Sources that have these
conditions present must be surveyed using
the instrument techniques of 4.3.1 or 4.3.2.
  Spray a soap solution over all potential
leak sources. The  soap solution may be a
commercially available leak detection
solution or may be prepared using
concentrated detergent and water. A pressure
sprayer or a squeeze bottle may be used to
dispense the solution. Observe the potential
leak sites to determine if any bubbles are
formed. If no bubbles are observed, the
source is presumed to have no detectable
emissions or leaks as applicable. If any
bubbles are observed, the instrument
techniques of 4.3.1 or 4.3.2 shall be used to
determine- if a leak exists, or if the source has
detectable emissions, as applicable.
  4.4 Instrument Evaluation Procedures. At
the beginning of the instrument performance
evaluation test, assemble and start up the
instrument according to the manufacturer's
instructions for recommended wannup period
and preliminary adjustments.
  4.4.1 Response Factor. Calibrate the
instrument with the reference compound as
specified in the applicable regulation. For
each organic species that is to be measured
during individual^ource surveys, obtain or
prepare a known  standard in air at a       _
concentration of approximately 80 percent of
the applicable teak definition unless limited
by volatility or explosivity. In these cases.
prepare a standard at 90 percent of the
saturation concentration, or 70 percent of the
lower explosive limit respectively. Introduce
this mixture to the analyzer and record the
observed meter reading. Introduce zero air
until a stable reading is obtained. Make a
total of three measurements by alternating
between the known mixture and zero air.
Calculate the response factor for each
repetition and the average response factor.
   Alternatively, if response factors have been
 published for the compounds of interest for
 the instrument or detector type, the. response
 factor determination is not required, and
 existing results may be referenced. Examples
 of published response factors for flame
 ionization and catalytic oxidation detectors
 are included in Section 5.
   4.43 Calibration Precision. Make a total of
 three measurements by alternately using zero
 gas and the specified calibration gas. Record
 the meter readings. Calculate the average
 algebraic difference between the meter
 readings and the known value. Divide this
 average difference by the known calibration
 value and mutiply by 100 to express the
 resulting calibration precision as a
 percentage.
                                                           '1-13

-------
          Federal Register / VoL 48. No. 161 /  Thursday. August ia 1983 / Rules and Regulations
4.4J Response Time. Introduce zero gas     Meter Reading of 10,000 ppmv for Selected       5.5 DuBoae, DJi* et al. Response of
to the instrument sample probe. When the    Organic Compounds. VS. Environmental      Portable VOC Analyzers to Chemical
*   *M*ed' •"* ****&    ****<* Agency. Research Triangle Park.     Mixtures, US. Environmental Protection
                              re the    N.C. Publication No. EPA 600/2-81-061.        AO.WV Rmu»rrJ. Tri.nol. P.* M r
                              t of the   Sept«nbar 1881.                           JSS^l^i£^i?£ .  K
                                                                                "Wi«««M« "»• EPA 800/2-81-lia September
aalatri>l*niteattamed.P«fonnthi.      BJ Bnwn. GJL. « aL RespoiiM Factors of
•tMqaanoemnetfaaeaandncordth*       VOC Analyaers Calibrated with Methane for
•aha. Calculate the average response tone.    Selected Organic Compounds. U.S.            |FRDoc.s»-a«sin*ds-ir-nsMi«m|
S. Bibliography.                          Environmental Protection Agency, Research    Ultra cnnsj ms ss •
3.1 DuBo~.Dj^ and OS. Harris.          Triangle Park. N.C. PnbHcatk» No, EPA 800/
      rPactonofVOCAnarjFwrsata       Z-81-OZ2. May 1981.
                                                    21-14

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          i* TJO NOT QUOTE OR CITE
        METHOD 23.  DETERMINATION OF HALOGENATED
            ORGANICS FROM STATIONARY SOURCES
                      INTRODUCTION
         Performance of this method should not be attempted
         by  persons unfamiliar with the operation of a gas
         chromatograph, nor by those who are unfamiliar with
         source  sampling because knowledge beyond the scope
         of  this  presentation is required.  Care must be
         exercised to  prevent exposure of sampling
         personnel to  hazardous emissions.
1.   Applicability and  Principle
     1.1   Applicability.  This method applies to the
measurement  of halogenated organics such as carbon tetra-
chloride, ethylene dichloride, perchloroethylene,
trichloroethylene, methylene chloride, 1,1,1-trichloroethane,
and trichlorotrifluoroethane  1n stack gases from sources as
specified in the regulations.  The method  does not measure
halogenated  organics  contained  in  particulate matter.
     1.2  Principle.   An  integrated bag  sample of stack gas
containing one or more halogenated organics  is subjected
to gas chromatographic (GC)  analysis, using a flame
ionization detector (FID).
2.  Range and Sensitivity
     The range of this method is  0.1  to  200 ppm.  The upper
limit may be extended by extending the  calibration  range or
by diluting the  sample.
                            23-1

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3.  Interferences
     The chromatograph column with the corresponding
operating parameters herein described normally provides an
adequate resolution of halogenated organics; however,
resolution interferences may be encountered in some sources.
Therefore, the chromatograph operator shall select the
column best suited to his particular analysis problem,
subject to the approval of the Administrator.  Approval
is automatic provided that confirming data are produced
through an adequate supplemental analytical technique,
e.g. analysis with a different column or GC/mass spectro-
scopy.  This confirming data must be available for review
by the Administrator.
4,  Apparatus
     4.1  Sampling (see Figure 23-1).  The sampling train
consists of the  following components:
     4.1.1  Probe.  Stainless steel, Pyrex* glass, or Teflon*
tubing (as stack temperature permits), each equipped with a
glass wool plug  to remove particulate matter.
     4.1.2  Sample Line.  Teflon, 6.4-mm outside diameter,
of sufficient length to connect probe to bag.  Use a new
unused piece for each series of bag samples that constitutes
an emission test, and discard upon completion of the test.
     *Mention of trade names or specific products does not
constitute endorsement by the Environmental Protection Agency.
                               23-2

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FILTER (GLASS WOOL)

             .PROBE
  TEFLON
SAMPLE LINE
VACUUM LINE
                     BALL
                    CHECKS
       QUICK
      CONNECTS
       (MALE)  U


               JE5  NO BALL
                   CHECKS
       	13 y
  T°fNlUICK-
      CONNECTS
      (FEMALE)
      r
   FLOW METER
                         TEDLAROR
                         ALUMINIZED
                         MYLAR BAG   /
                           RIGID LEAK-PROOF
                             CONTAINER
                             CHARCOALTUBE
                                                PUMP
 Figure 23-1. Integrated-bag sampling train. (Mention of trade names
 or specific products does not constitute endorsement by the Environ-
 mental Protection Agency.)
                           23-3

-------
     4.1.3  Quick Connects.   Stainless steel,  male (2)  and
female (2), with ball  checks (one pair without), located
as shown in Figure 23-1.
     4.1.4  Tedlar or Aluminized Mylar Bags.  100-liter
capacity, to contain sample.
     4.1.5  Bag Containers.   Rigid leakproof containers
for sample bags, with covering to protect contents from
sunlight.
     4.1.6  Needle Valve.  To adjust sample flow rate.
     4.1.7  Pump.  Leak-free, with minimum of 2-liters/min
capacity.
     4.1.8 Charcoal  Tube,   TO  prevent admission  of
 halogenated organlcs  to the atmosphere in the vicinity
 of samplers.
      4.1.9 plow Meter,   For observing sample flow rate;
 capable of measuring  a  flow range from 0.10 to  1.00 Iiter/m1n.
      4.1.10  Connecting Tubing.  Teflon, 6,4-mm outside
 diameter,  to  assemble sampling  train  (Figure  23-1).
      4,2  Sample Recovery.   Teflon  tubing,  6.4-mm outside
 diameter,  to  connect  bag to gas chromatograph sample loop
 1s required for sample  recovery. Use a  new unused piece
 for each series of bag  samples  that constitutes an emission
 test and discard upon conclusion of analysis  of those  bags.
                               23-4

-------
     4.3.   Analysis.   The following equipment  is  needed:
     4.3.1   Gas Chromatograph.   With FID,  potentiometric
strip chart recorder,  and 1.G-  to 2.0-ml  sampling loop
in automatic sample valve.   The chromatographic  system
shall be capable of producing a response  to 0.1  ppm of
the halogenated organic compound that is  at least as
great as the average noise level.  (Response is  measured
from the average value of the baseline to the  maximum of
the waveform, while standard operating conditions are in
use.)
     4.3.2  Chromatographic Column.  Stainless steel,
3.05 m by 3.2 mm, containing 20 percent SP-21CO/0.1 percent
Carbowax 1500 on 100/120 Supelcoport.  The analyst may  use
other columns provided that the precision and accuracy  of
the analysis of standards are not impaired and he has
available for review information confirming that there  is
adequate resolution of the halogenated organic compound
peak.   (Adequate resolution is  defined as an area overlap
of not more  than 10 percent of the halogenated organic
compound peak by an interferent  peak.  Calculation of
area overlap is explained in Appendix E, Supplement A:
"Determination of Adequate Chromatographic Peak Resolution."
     4.3.3   Flow Meters  (2).   Rotameter type,
O-to-100-ml/min capacity.
                               23-'

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     4.3.4  Gas Regulators.   For required gas  cylinders.
     4.3.5  Thermometer.   Accurate to 1°C, to  measure
temperature of heated sample loop at time of sample
injection.
     4,3,6  Barometer.  Accurate to 5 mm Hg, to measure
atmospheric pressure around gas chromatograph during
sample analysis.
     4.3.7  Pump.  Leak-free, with a minimum of 100-ml/min
capacity.
     4.3.8  Recorder.  Strip chart type, optionally
equipped  with  either disc or electronic integrator.
     4.3.9  planimeter.  Optional, in place of disc or
electronic  integrator  (4.3.8),  to measure chromatograph
peak areas.
     4.4  Calibration,  Sections 4.4.2 through 4.4.6 are
for  the optional procedure in Section 7.1.
     4.4.1  Tubing.  Teflon, 6.4-mra outside diameter,
separate  pieces marked for each calibration concentration.
     4,4.2  Tedlar or Aluminized Mylar Sags.  50-liter
capacity, with valve; separate  bag marked for each
calibration concentration.
     4.4.3  Syringe,  25-yl, gas tight, individually
calibrated, to dispense liquid  halogenated organic solvent.
                               23-6

-------
     4.4.4  Syringe.   50-vil,  gas tight, individually
calibrated to dispense liquid halogenated organic solvent.
     4.4.5  Dry Gas Meter, with Temperature and Pressure
Gauges.  Accurate to +_ 2 percent, to meter nitrogen in
preparation of standard gas mixtures, calibrated at the
flow rate used to prepare standards.
     4.4.6  Midget Impinger/Hot Plate Assembly.  To
vaporize solvent.
5.  Reagents
     It is  necessary  that all  reagents  be  of chromatographic
grade.
     5.1  Analysis.   The  following  are needed  for  analysis:
     5.1.1   Helium Gas  or Nitrogen  Gas.  Zero  grade,  for
chromatographic  carrier gas.
     5.1.2   Hydrogen  Gas,  Zero grade.
      5.1.3   Oxygen Ga,s  or Air.  Zero grade, as required by
 the detector.
      5.2  Calibration.   Use  one of the following options:
 either 5.2.1 and 5.2.2, or 5.2.3.
      5.2.1   Halogenated Organic Compound, 99 Mol Percent
 Pure.   Certified by the manufacturer to contain a minimum
 of 99 Mol percent of the particular halogenated organic
 compound; for use in the preparation of standard gas
 mixtures as described in Section 7.1.
                               23-7

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     5.2.2 Nitrogen Gas.   Zero grade, for preparation
of standard gas mixtures  as described in Section 7.1.
     5.2.3  Cylinder Standards (3).  Gas mixture standards
(200, TOO, and 50 ppm of the halogenated organic compound
of interest, in nitrogen).  The tester may use these
cylinder standards to directly prepare a chromatograph
calibration curve as described in Section 7.2.2, if the
following conditions are met:  (a)  The manufacturer
certifies the gas composition with an accuracy of
£3  percent or better (see Section 5.2.3.1),
 (b)  The manufacturer recommends a maximum shelf life over
which  the  gas  concentration  does not change by greater than
+ 5  percent from the certified value,   (c)  The manufacturer
affixes the date of gas  cylinder preparation, certified
concentration  of the halogenated organic compound, and
 recommended maximum shelf life to  the cylinder before shipment
from the gas manufacturer to the buyer.
     5.2.3.1   Cylinder Standards Certification.  The
manufacturer shall  certify the concentration of the  halogenated
organic compound in nitrogen in each cylinder by  (a) directly
 analyzing  each cylinder  and  (b) calibrating his analytical
 procedure  on the day of  cylinder analysis.  To calibrate
 his  analytical  procedure, the manufacturer shall use, as
 a minimum, a  three-point calibration curve. It  is  recommended
 that the  manufacturer maintain {I) a high-concentration
                               23-8

-------
calibration standard (between 200 and 400 ppm)  to  prepare
his calibration curve by an appropriate dilution
technique and (2)  a low-concentration calibration
standard (between  50 and 100 ppm) to verify the dilution
technique used.  If the difference between the  apparent
concentration read from the calibration curve and
the true concentration assigned to the low-concentration
calibration standard exceeds 5 percent of the true concen-
tration, the manufacturer shall determine the source of
error and correct it, then repeat the three-point  calibration.
     5.2.3.2  Verification of Manufacturer's Calibration
Standards.  Before using, the manufacturer shall  verify  each
calibration standard by (a) comparing it to gas mixtures
prepared (with 99 Mol percent of the halogenated organic
compounds) in accordance with the procedure described in
Section 7.1 or by  (b) having it analyzed by the National
Bureau of Standards, if such analysis is available.  The
agreement between  the initially determined concentration
value and the verification concentration value must be
within + 5 percent.  The manufacturer must reverify all
calibration standards on a time  interval consistent with the
shelf life of  the  cylinder standards  sold.
     5.2.4  Audit  Cylinder Standards  (2).  Gas mixture
standards with concentrations  known  only to the person

-------
supervising the analysis samples.  The audit cylinder standards
shall be identically prepared as those in Section 5.2.3 (the
halogenated organic compounds of interest, in nitrogen).   The
concentrations of the audit cylinders should be:  one
low-concentration cylinder in the range of 25 to 50 ppm,  and
one high-concentration cylinder in the range of 200 to 300 ppm.
When available, the tester may obtain audit cylinders by
contacting:  Environmental Protection Agency, Environmental
Monitoring and Support Laboratory, Quality Assurance Branch
(MO-77), Research Triangle Park. North Carolina 27711.  If audit
cylinders are not available at the Environmental Protection
Agency, the tester must secure an alternative source.
6.   Procedure
     6.1  Sampling.  Assemble the sampling train as shown in
Figure 23-1.  Perform a bag leak check according to Section 7.3.2.
Join the quick connects as Illustrated, and determine that all
connections between the bag and the probe are tight.  Place the
end of the probe at the centroid of the stack and start the
pump with the needle valve adjusted to yield a flow that will
more than half fill the bag in the specified sample period.
After allowing sufficient time to purge the line several  times,
connect the vacuum line to the bag and evacuate the bag until
the rotameter Indicates no flow.  At all times, direct the gas
exiting the rotameter away from sampling personnel.
                               23-'0

-------
Then reposition the sample and vacuum lines and begin  the
actual sampling, keeping the rate constant.  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.  Protect bag container from sun-
light,
     6.2  Sample Storage.  Keep the sample bags out of direct
sunlight and protect from heat.  Perform the analysis  within
1 day of sample collection for methylene chloride, ethylene
dichloride, and trichlorotrifluoroethane, and within 2 days
for perchloroethylene, trichloroethylene, 1,1,1-trichloro-
ethane, and carbon tetrachloride.
     6.3  Sample Recovery.  With a new piece of Teflon
tubing identified for that bag, connect a bag inlet valve
to the gas chromatograph sample valve.  Switch the valve
to receive gas from the bag through the sample loop.
Arrange the equipment so the sample gas passes from the
sample valve to a O-to-100-ml/min rotameter with flow
control valve followed by a charcoal tube and a
0-to-l-in. HpO pressure gauge.  The tester may maintain  the
sample flow either by a vacuum pump or container pressur-
ization if the collection bag remains in the rigid container.
After sample loop purging is ceased, allow the pressure  gauge
to return to zero before activating the gas sampling valve.
                             23-11

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     6.4  Analysis.  Set the column temperature to 100°C
and the detector temperature to 225°C.  When optimum hydrogen
and oxygen flow rates have been determined, verify and main-
tain these flow rates during all chromatograph operations.
Using zero helium or nitrogen as the carrier gas, establish
a flow rate 1n the range consistent with the manufacturer's
requirements for satisfactory detector operation.  A flow
rate of approximately 20 ml/rain should produce adequate
separations.  Observe the base line periodically and determine
that the noise level has stabilized and that base-line drift
has ceased.  Purge the  sample loop for 30  sec at the rate of
TOO ml/urin, then activate the sample  valve.  Record the
injection  time  (the  position of the pen on the chart at the
time of sample  injection},  the  sample number, the sample
loop temperature,  the column temperature,  carrier gas flow
rate,  chart speed, and  the  attenuator setting.  Record the
barometric pressure.  From  the  chart, note the peak having
the retention time corresponding  to the halogenated organic
compound,  as determined in  Section 7.2.1.  Measure the
halogenated organic  compound peak area, Am,  by use of a disc
integrator,  electronic  integrator, or a planimeter.  Record
A  and the retention time.   Repeat the  injection  at least
two times  or until two  consecutive values  for  the total area
of the peak do  not vary more than 5  percent.  Use the average
value  for  these two  total areas to compute the bag concentration.
                                23-li

-------
     6.5  Determination  of  Bag Water  Vapor  Content.
Measure the ambient  temperature  and barometric  pressure
near the bag.   From  a  water saturation  vapor  pressure
table, determine and record the  water vapor content  of
the bag as a decimal figure.  (Assume the relative
humidity to be 100 percent  unless a lesser value is  known.)
7.  Preparation of Standard Gas  Mixtures, Calibration, and
    Quality Assurance
     7,1  Preparation of Standard Gas Mixtures.  (Optional
procedure—delete if cylinder standards are used.)  Assemble
the apparatus shown in Figure 23-2.   Check that all  fittings
are tight.  Evacuate a 50-liter Tedlar  or aluminized Mylar
bag that has passed a leak check (described in Section 7.3.2)
and meter in about  50 liters of nitrogen.  Measure the
barometric pressure, the relative pressure at the dry gas
meter,  and the temperature at the dry gas meter.  Refer to
Table 23-1.  While  the bag  is filling,  use the  50-yl  syringe
to  inject through the septum on top of the impinger,  the
quantity  required to yield  a concentration of 200 ppm.  In a
like  manner,  use  the 25-ul  syringe to  prepare bags  having
approximately  100-  and  50-ppm concentrations.   To calculate
the specific  concentrations, refer to  Section 8.1.  (Tedlar
bag gas mixture  standards  of methylene chloride,  ethylene
dichloride,  and  trichlorotrifluoroethane may be used  for
                               23-3

-------
                    TEDLAfi SAG
                     CAPACITY
                       SOIitm
Figure 23-2. Preparation of standards (optional).

-------
TABLE 23-1.  INJECTION VALUES FOR PREPARATION OF STANDARDS (Optional,  See  Section  7.1)
Compound
Molecular   Density at
Weight         293°K
g/g-mole        g/ml
pi/50 liters of N2 required
for approximate concentration of:
200 ppm      100 ppm      50 ppm
Perchloroethylene C,,C14
Trichloroethylene C2HCU
1,1,1-Trlchloroethane C2H3C13
Methyl ene Chloride CH2C12
Tr1chlorotr1fluoroethane C2C13I
Carbon Tetrachlorlde CCK
Ethylene Dichlorlde C2H4C1?
165.85
131.40
133.42
84.94
F3 187.38
153.84
98.96
1.6230
1.4649
1.4384
1.3255
1.5790
1.5940
1.2569
42.5
37.3
38.6
26.6
49.3
40.1
32.7
21.2
18.6
19.3
13.3
24.7
20.1
16.4
10.6
9.3
9.6
6.7
12.3
10.0
8.2

-------
1  day, trichloroethylene and 1,1,1-trichloroethane for
2 days, and perch!oroethylene and carbon tetrachloride
for 10 days from the date of preparation.  (Caution:   If the
new gas mixture standard is a lower concentration than the
previous gas mixture standard, contamination may be a problem
when a bag is reused.)
     7.2  Calibration.
     7.2.1  Determination of Halogenated Organic Compound
Retention Time.  (This section can be performed simultaneously
with  Section 7.2.2.)  Establish chromatograph conditions
 Identical with  those  in  Section 6.4, above.  Determine proper
 attenuator  position.  Flush the  sampling loop with zero
 helium or nitrogen and  activate  the sample  valve.  Record the
 Injection time, the sample  loop  temperature, the  column
 temperature,  the carrier gas flow rate,  the chart speed, and
 the attenuator  setting.   Record  peaks and detector responses
 that occur  in the  absence of the halogenated organic.  Main-
 tain conditions (with the equipment plumbing arranged  identi-
 cally to Section 6.3),  flush the sample loop for  30  sec at
 the rate of 100 ml/min  with one  of the  halogenated organic
 compound calibration  mixtures, and activate the sample valve.
 Record the injection  time.   Select the  peak that  corresponds
 to the halogenated organic  compound.  Measure  the distance
 on the chart from the Injection  time  to the time at  which
 the peak maximum occurs.  This  distance divided by the chart
                              23-16

-------
speed is defined as the halogenated organic compound  peak
retention time.  Since it is possible that there will  be
other organics present in the sample, it is very important
that positive identification of the halogenated organic
compound peak be made.
     7.2.2  Preparation of Chromatograph Calibration  Curve.
Make a gas chromatographic measurement of each standard gas
mixture (described in Section 5,2.3 or 7.1) using conditions
identical with those listed in Sections 6.3 and 6.4.   Flush
the sampling loop for 30 sec at the rate of 100 ml/min with
one of the standard gas mixtures and activate the sample
valve.  Record GC, the concentration of halogenated organic
injected, the attenuator setting, chart speed, peak area,
sample loop temperature, column temperature, carrier gas
flow rate, and retention time.  Record the laboratory
pressure.  Calculate AC, the peak area multiplied by the
attenuator setting.  Repeat until two consecutive injection
areas are within 5 percent, then plot the average of those
two values versus CG.  When the other standard gas mixtures
have been similarly analyzed and plotted, draw a straight
line through the points derived by the least squares method.
Perform calibration daily, or before and after each set  of
bag samples, whichever is more frequent.
                             23-17

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     7.3  Quality Assurance.
     7.3.1  Analysis Audit.  Immediately after the preparation
of the calibration curve and prior to the sample analyses,
perform the analysis audit described in Appendix E, Supplement B:
"Procedure for Field Auditing GC Analysis."
     7.3.2  Bag Leak Checks.  While performance of this section
is required subsequent to bag use, it is also advised that  it
be performed prior to bag use.  After each use, make sure a bag
did not develop leaks by connecting a water manometer and
pressurizing the bag to 5 to 10 cm H20 (2 to 4 in. H20).
Allow to  stand for 10 min.  Any displacement in the water
manometer indicates a leak.  Also, check the rigid container
for leaks In this manner.   (Note:  An alternative leak
check method 1s to pressurize the bag to 5 to 10 cm H~0
(2 to 4 in. H20) and allow to stand overnight.  A deflated
bag indicates a leak.)  For each sample bag in its rigid
container, place a rotameter in line between the bag and
the pump  inlet.  Evacuate the bag.  Failure of the rotameter
to register zero flow when the bag appears to be empty
indicates  a leak.
8.  Calculations.
     8.1   Optional Procedure Standards Concentrations.
Calculate each halogenated organic standard concentration
(Cc in ppn) prepared in accordance with Section 7.1 as follows:
                              23-18

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            22. (24.055 x 103)                .   BD  T
     GC  =  fl	  =  6<240 x 1Q4   M v  "  p
              v  v 291  JL                     'mm
               m T Tm   760"
                                            Eq. 23-1
Where:
     B      =  Volume of halogenated organic injected, pi.
     D      =  Density of compound at 293°K, g/ml.
     M      =  Molecular weight of compound, g/g-mole.
     V      =  Gas volume measured by dry gas meter,  liters.
     Y      =  Dry gas meter calibration factor, dimensionless.
     P      *  Absolute pressure of dry gas meter,  mm Hg.
     T      »  Absolute temperature of dry gas meter, °K.
     24.055 »  Ideal gas molal  volume at 293°  K and 760 mm Hg,
               Uters/g-mole.
      103    =  Conversion factor. [{ppm)(ml)]/yl.
      8.2  Sample  Concentrations.  From the calibration curve
 described in Section 7.2.2 above, select the value of CG that
 corresponds  to A  .  Calculate  GS, the concentration of
 halogenated  organic in  the sample  (in  ppm), as follows:
             C  P  T
      c   ,  c r 1                                Eq.  23-2
       s      «     C1-S>
                              23-19

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Where:
     C    »  Concentration of the halogenated organic
             indicated by the gas chromatograph, ppm.
     P    «  Reference pressure, the laboratory pressure
             recorded during calibration, mm Hg.
                                    i
     Tj   »  Sample loop temperature at the time of
             analysis, °K.
     PJ   •  Laboratory pressure at time of analysis, mm Hg.
     T    »  Reference temperature, the sample loop temper-
             ature recorded during calibration, °K.
     Swb  *  Water vaP°r content of the bag sample, volume
             fraction.
9.  References
     1.  Feairheller, W.R., A.M. Kemmer, B.J. Warner, and
D.Q. Douglas.  Measurement of Gaseous Organic Compound
Emissions by Gas Chromatography.  EPA Contract No.  68-02-1404,
Task 33 and 68-02-2818, Work Assignment 3.  January 1978.
Revised by EPA August 1978.
     2. Supelco, Inc.  Separation of Hydrocarbons.
Bulletin 747.  Belleforte, Pennsylvania.  1974.
     3.  Communication from Joseph E. Knoll.  Perch!oroethylene
Analysis by Gas Chromatography.  March 8, 1978.
     4.  Communication from Joseph E. Knoll.  Test  Method for
Halogenated Hydrocarbons.  December 20, 1978.
                              23-20

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40 CFR Part 60 Appendix A
Final, promulgated  10/3/80
45 FR 65958
Revised 1/27/83
         METHOD 24--DETERMINATION OF VOLATILE MATTER CONTENT,  WATER
   CONTENT,  DENSITY,  VOLUME SOLIDS,  AND WEIGHT SOLIDS OF SURFACE  COATINGS

1.   Applicability and Principle


     1.1   Applicability.   This method applies to the determination  of volatile

matter content, water content, density, volume solids, and weight solids  of

paint, varnish, lacquer,  or related  surface coatings.

     1.2   Principle.   Standard methods are used to determine the  volatile

matter content, water content, density, volume solids, and weight solids  of

the paint, varnish, lacquer, or related surface coatings.

2.   Applicable Standard Methods

     Use  the apparatus, reagents, and procedures specified in the standard

methods below:

     2.1   ASTM D 1475-60 (Reapproved 1980).  Standard Test Method for Density

of Paint, Lacquer, and Related Products (incorporated by  reference - see §60.17)

     2.2   ASTM D 2369-81.  Standard Test Method for  Volatile  Content of Paints

(incorporated by reference -  see §60.17).

     2.3  ASTM D 3792-79.  Standard Test Method for  Water Content in Water

Reducible Paint  by Direct  Injection  into a Gas  Chromatograph  (incorporated by

reference - see  §60.17).

     2.4  ASTM D 4017-81.  Standard  Test Method for  Water in  Paints  or Paint

Materials by  the Karl  Fischer Titration Method  (incorporated  by  reference -

see  §60.17).
                                     24-1

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3.  Procedure



     3.1  Volatile Matter Content.   Use the procedure in ASTM D 2369-81 (in-



corporated by reference - see §60.17) to determine the volatile matter content



(may include water) of the coating.   Record the following information:



     Wj = Weight of dish and sample  before heating, g.



     VL = Weight of dish and sample  after heating, g.



     W- =  Sample weight, g.



Run analyses in pairs (duplicate sets) for each coating until the criterion



in section 4.3 is met.  Calculate the weight fraction of the volatile matter



(W ) for each analysis as follows:


                              W, -  W~
                         Wv • -                                  *>• "-1




Record the arithmetic average (W ).



     3.2  Water Content.  For waterborne (water reducible) coatings only,



determine the weight fraction of water (W )  using either "Standard Test Method



for Water Content in Water Reducible Paint by Direct Injection into a Gas



Chromatograph" or "Standard Test Method for  Water in Paint or Related Coatings



by the Karl  Fischer Titration Method."  (These two methods are incorporated



by reference - see §60.17.)  A waterborne coating is any coating which contains



more than 5  percent water by weight in its volatile fraction.  Run duplicate



sets of determinations until the criterion in section 4.3 is met.  Record the



arithmetic average (W ).
                     W


     3.3  Coating Density.  Determine the density (D , kg/liter) of the sur-



face coating using the procedure in ASTM D 1475-60 (incorporated by reference



- see §60.17).
                                    24-2

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Run duplicate sets of determinations for each coating until  the
criterion in section 4.3 is met.  Record the arithmetic average  (D  ).
     3.4  Solids Content.  Determine the volume fraction (V  )  solids
of the coating by calculation using the manufacturer's formulation.
4.  Data Validation Procedure
     4.1  Summary.  The variety of coatings that may be subject  to
analysis makes it necessary to verify the ability of the analyst
and the analytical procedures to obtain reproducible results for the
coatings tested.  This is done by running duplicate analyses on
each sample tested and comparing results with the within-laboratory
precision statements for each parameter.  Because of the inherent
increased imprecision in the determination of the VOC content of
waterborne coatings as the weight percent water increases, measured
parameters for waterborne coatings are modified by the appropriate
confidence limits based on between-laboratory precision statements.
     4.2  Analytical Precision Statements.  The within-laboratory and
between-laboratory precision statements are given below:

                              Wi thi n-1aboratory   Between-!aboratory
Volatile Matter  Content, Wy         1.5% Wv              4.7% Wy
Water  Content, 1^                  2.9% V/w              7.5% WM
Density, D                          0.001  kg/liter       0.002 kg/liter
                            24-3

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     4.3  Sample Analysis  Criteria.   For Wy  and NW,  run duplicate
analyses until  the difference between the two values 1n a set is
less than or equal to the  within-laboratory  precision statement for
that parameter.  For DC run duplicate analyses until each value in a
set deviates from the mean of the set by no  more than the within-
laboratory precision statement.  If after several attempts it is
concluded that the ASTM procedures cannot be used for the specific
coating with the established within-laboratory precision, the
Administrator will assume responsibility for providing the necessary
procedures for revising the method or precision statements upon written
request to:  Director, Emission Standards and Engineering Division,
 tMD-13) Office of Air  Quality  Planning  and  Standards,  U.S. Environmental
 Protection Agency, Research  Triangle Park,  North Carolina  27711.
      4.4  Confidence Limit Calculations for Waterborne Coatings.  Based
 on the between-laboratory precision  statements, calculate the confidence
 limits for waterborne  coatings as follows:
      To calculate the  lower  confidence  limit,  subtract the appropriate
 between-laboratory precision value from the measured mean value for
 that parameter.   To calculate  the upper confidence  limit, add  the
 appropriate between-laboratory precision value to the  measured mean
 value for that parameter.  For Wy  and DC, use the lower confidence
 limits, and for Ww, use the upper confidence limit. Because V  is
                  w                                            *
 calculated, there is no adjustment for  the  parameter.
                                   24-4

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5.  Calculations
     5.1  NOnuC;J«jOui VO.ut'i lo i'iut'C
            oO ivtnc~uotTic
Where:
     v,'0  =  Weight fraction  nor.aqueoui, volatile matter,  g/g.

     5.1.2  V.aterbcrne Coatings.
                                   ''o  ~  v'v " ww       Eq-  24'
     r o  * * — - — v.'. ^^» —.  *
      i.e.  weiwHi. irucc.on  ^o
o. L  ,;u i a
                              •.(_-•
                                                  «^s
                                   A'   =  : - n        Eq.  24-4
!Xhcre:  V.'   =  Weight sol-ids,  g/g.
         ^
2.  3i Dl locrap'v
     5.1  Provisional i'iothou Test for Yo'icUilu Content  of  Paints.
Available from:  Chairrr.ur,,  Ccrraittce D-! on Puint dr.d Delated
COutir.gs and Koterials, P-nericdn Society for Testing and Materials,
1915 Race Street, Philadelphia,  Pennsylvania 19103.  ASTM
Designation D 23oS-31.
     5.2  Standard Method of Test for Density of Paint, Varnish,
Lacc,j£r, and Related Products.  In:   1974 Bock of ASTM  Standards,
Part 27.  Pniladelp'Via, Pennsylvania, ASTM Designation  D 1475-60.
"SCO.
                                     24-5

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     6.3  Standard Method of Test for Water in  Water Reducible
Paint by Direct Injection into a Gas Chromatograph.   Available
from:  Chairman, Committee D-l on Paint and Related  Coatings
and Materials, American Society for Testing and Materials,  1916
Race Street, Philadelphia, Pennsylvania 19103.   ASTM Designation
D 3792-79.
     6.4  Provisional Method of Test Water in Paint  or Related
Coatings by the Karl Fischer Tltration Method.   Available from:
Chairman, Committee D-l on Paint and Related Coatings and Materials,
American Society for Testing and Materials, 1916 Race Street,
Philadelphia,  Pennsylvania 19103.
                                 24-6

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         F«aW«l Kegfatot / Vol. 45. No. 194  /  Friday.  October 9. I960 / Rules  and Regulations
Urthml a*—Determination of Volant* Matte
Calir. Wetet Content. Density. Volume
Said*, sod Weight Solids of Surface Coating*

L Applicability and Principle
  1.1  Applicability. This method applies to
the determination of volatile matter content
water content, density, volume solids, and
weight lolidi of paint, varnish, lacquer, or
related turface coatings
  1.2  Principle. Standard methods are used
to determine the volatile matter content
water content density, volume solids, and
weight solids' of the paint varnish, lacquer, or
related surface roarings.

I Applicable Standard Methods
  Use the apparatus, reagents, and
Itaeedum specified in the standard method*
fialnaaj-
  2.1   ASTM D1475-40. Standard Method of
Test for Density of Paint Lacquer, and
Related Products.
   24   ASTM D 2380-81. Provisional Method
of Test for Volatile Content of Paint*.
   U   ASTM D37W-79. Standard Method of
Test for Water in Water Reducible Paint by
 Direct Infection into a Gas Chromatograph.
   14  ASTM Provisional Method of Test for
 Watsr In Paint or Related Coatings by tb*
 Kari Fischer Titration Method.

 JL Proctdun
   3.1  Volatile Matter Content Use the
 procedure in ASTM D 238B-81 to determine
 fct volatile matter content (may include
 waterj of the coating. Record the following
 IsfanMtion:
 Wi-Weight of dish and sample before
    heating, g.
 Wi- Weight of dish and sample after healing,

 W.-Sample Weight g.
 ton analyses in pairs (duplicate sets) for
 each coating until the criterion in section 4J
 b out Calculate the weight fraction of mat
  volatile matter (W.) for each analysis as
           v-
                            Eq.  24-1
Record th* arithmetic average (W.).
                                            3.2  Water Content For walartxane (water
                                           reducible) coatings only, determine the
                                           weight fraction of water (W,) using either
                                           '•Standard Method of Test for Water in Water
                                           Reducible Paint by Direct Injection into a Gas
                                           Chromatograph" or "Provisional Method of
                                           Test for Water in Paint or Related Coatings
                                           by the Karl Fischer Tltratian Method." A
                                           waterbame coating is any coating which
                                           contains more than 6 percent water by weight
                                           in Its volatile fraction. Run duplicate seta of
                                           determinations
-------
40 CFR Part 60,  Appendix A
Final, Promulgated
                METHOD 24A--DETERMINATION  OF VOLATILE MATTER CONTENT
                 AND DENSITY  OF PRINTING  INKS AND RELATED COATINGS
 1.   Applicability and Principle
      1.1  Applicability.  This method  applies  to the  determination  of
 the volatile organic compound (VOC) content and  density  of  solvent-borne
 (solvent reducible) printing inks or related coatings.

      1.2  Principle.  Separate procedures are  used  to determine  the VOC
 weight fraction and density of the coating and the  density  of the solvent
 in the coating.  The VOC weight fraction is determined by measuring the
 weight loss of a known sample quantity which has  been heated  for a
 specified length of time at a specified temperature.  The density of
 both the coating and solvent are measured by a standard  procedure.   From
 this information,  the VOC volume fraction is calculated.
 2.   Procedure
      2.1  Weight Fraction VOC.
      2.1.1  Apparatus.
      2.1.1.1  Weighing Dishes.   Aluminum foil, 58 mm in diameter by
 18 mm high,  with a flat bottom.   There must be at least three weighing
 dishes  per sample.
      2.1.1.2  Disposable syringe,  5 ml.
      2.1.1.3  Analytical  Balance.   To measure to within 0.1 mg.
      2.1.1.4  Oven.   Vacuum oven capable of maintaining a temperature of
 120 ±2°C and an absolute pressure of 510 ±51 mm Hg  for 4 hours.   Alternatively,
                                      24A-1

-------
a forced draft oven capable of maintaining a temperature of 120 =2°C
for 24 hours.
     2.1.1.5  Analysis.   Shake or mix  the sample thoroughly to assure
that all the solids are  completely  suspended.   Label and weigh to the
nearest 0.1 mg a weighing dish and  record this  weight (Mxl).
     Using a 5-ml  syringe without  a needle remove  a  sample of the coating,
Weigh the syringe  and sample  to  the nearest  0.1 mg and record this
weight  (M Y1).   Transfer 1 to 3  g  of the sample to the tared weighing
dish.   Reweigh  the syringe and sample to the nearest 0.1 mg and  record
this  weight {M  y2).  Heat the weighing dish  and sample in a vacuum  oven
 at an absolute pressure of 510 ± 51 mm Hg and a temperature of 120  ± 2°C
 for 4 hours.  Alternatively, heat the weighing dish  and  sample in a
 forced draft oven at a temperature of 120 ±  2° C  for 24  hours.   After
 the weighing dish has cooled, reweigh it to  the nearest  0.1 mg and
 record the weight {M «).  Repeat this procedure for  a  total of three
 detenninations for each  sample.
      2.2  Coating Density.  Determine the density of the ink  or  related
 coating according to the procedure outlined in ASTM  D  1475-60, which  is
 incorporated by reference.  Make a total of three determinations for
 each coating.  Report the density "5^ as the arithmetic average of the
 three determinations.   This Standard Test Method For Density  of  Paint,
 Varnish, Lacquer,  and Related Products  can be  found in the "1974 Annual
 Book of ASTM Standards." It is available from the American Society for
 Testing and Materials,  1916 Race Street, Philadelphia, Pennsylvania
 19103. It is also  available for inspection at  the Office of the  Federal
                                      24A-2

-------
Register  Information  Center,  Room 8301,  1100 L Street, N.W., Washington,
D.C.  20408.   This  incorporation by reference was approved by the Director
gf the  Federal  Register on _ , 1981.  This material is incorporated
as it exists  on the date of the approval and a notice of any change in
these materials will  be published in the FEDERAL REGISTER.
     2.3   Solvent  Density.  Determine the density of  the solvent according
•to the  procedure outlined in ASTM D 14-75-60.  Make a  total  of three
determinations for each coating.  Report the density"^ as the arithmetic
average of the three determinations.
 3.  Calculations
     3.1  Weight Fraction VOC.   Calculate the weight  fraction volatile
organic content W  using  the following  equation:

                             " MrY7  " \?
                                      —                  Eq. 24A-1
                        McYl  " McY2
     Report the weight  fraction  VOC  W~*  as the arithmetic average of the
 three determinations.
     3.2  Volume  Fraction  VOC.   Calculate the volume fraction volatile
 organic content VQ  using  the following equation:
                w~~  "b~~
          v   =  __2 - £.                                   Eq. 24A-2
                                      24A-3

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4.   Bibliography
     4.1  Standard Test Method for Density of Paint,  Varnish,  Lacquer,
and Related Products.  In:  1974 Book of ASTM Standards,  Part  25,  Philadelphia,
Pennsylvania, ASTM Designation D 1475-60.  1974.  p.  231-233.
     4.2  Tel conversation.  Wright, Chuck, Inmont Corporation with
Reich, R.A*, Radian Corporation.  September 25, 1979.   Sravure Ink
Analysis.
     4.3  Teleconversation.  Oppenheimer, Robert, Gravure Research
Institute with Burt, Rick, Radian Corporation.  November  5,  1979.
Gravure  Ink  Analysis.
                                     24A-4

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             Federal Register  / Vol. 47, No. 216 /  Monday.  November  8.  1982 / Rules  and Regulations
 Appendix A—Reference Methods
 Method 24A—Determination of Volatile
 Matter Content and Density of Printing Inks
 and Related Coatings
   1. Applicability and Principle,
   1.1  Applicability. This method applies to
 the determination of the volatile organic
 compound (VOC) content and density of
 solvent-borne (solvent reducible) printing
 inks or related coatings.
   1.2  Principle. Separate procedures are
 used to determine the VOC weight fraction
 and density of the coating and the density of
 the solvent in the coating. The VOC weight
 fraction is determined by measuring the
 weight loss of a known sample quantity
 which has been heated for a specified length
 of time at a specified temperature. The
 density of both the coating and solvent are
 measured by a standard procedure. From this
 information, the VOC volume fraction is
 calculated.
   2. Procedure.
   2.1  Weight Fraction VOC.
   2.1.1  Apparatus.
   2.1.1.1  Weighing Dishes. Aluminum foil,
 58 mm in diameter by 18 mm high,  with a flat
 bottom. There must be at least three weighing
 dishes per sample.
   2.1.1.2  Disposable syringe, 5 ml.
   2.1.1.3  Analytical Balance. To measure to
 within 0.1 mg.
   2.1.1.4  Oven. Vacuum oven capable of
 maintaining a temperature of 120±2'C and
 an absolute pressure of 510 ±51 mm Hg for 4
 hours. Alternatively, a forced draft oven
 capable of maintaining a temperature  of 120
 ±2°C for 24 hours.
  2.1.1.5   Analysis. Shake or mix the sample
 thoroughly to assure that all the solids are
completely suspended. Label and weigh  to
the nearest 0.1  mg a weighing dish and record
this weight (M,,).
   Using a 5-ml syringe without a needle
 remove a sample of the coating. Weigh the
 syringe and sample to the nearest 0.1 mg and
 record this weight (MeYi). Transfer 1 to 3 g of
 the sample to the tared  weighing dish.
 Reweigh the syringe and sample to the
 nearest 0.1 mg and record this weight (McYz).
 Heat the weighing dish and sample in a
 vacuum oven at an absolute pressure of 510
 ±51 mm Hg and a temperature of 120 ±2'C
 for 4 hours. Alternatively, heat the weighing
 dish and sample in a forced draft oven at a
 temperature of 120 ±2°C for 24 hours. After
 the weighing dish has cooled, reweigh it to
 the nearest 0.1 mg and record the weight
 (M,j). Repeat this procedure for a total of
 three determinations for each sample.
   2.2  Coating Density. Determine the
 density of the ink or related coating
 according to the procedure outlined in ASTM
 D1475-60 (Reapproved 1980), which is
 incorporated by  reference. It is available
 from the American Society of Testing and
 Materials, 1916 Race Street, Philadelphia,
 Pennsylvania 19103. It is also available for
 inspection at the Office of the Federal
 Register, Room 8401,1100 L Street, NW.,
 Washington, D.C. This incorporation by
 reference was approved by the Director of
 the Federal Register on November 8,1982.
 This material is incorporated as it exists on
 the date of approval and a notice of any
 change in these materials will be published in
 the Federal Register.
  2.3  Solvent Density. Determine the
 density of the solvent according to the
 procedure outlined in ASTM D1475-60
 (reapproved 1980). Make a total of three
 determinations .for each coating. Report the
 density D. ds1 thtrBrithmetic average of the
 three determinations.
  3. Calculations.
  3.1  Weight Fraction VOC. Calculate the
weight fraction volatile organic content W.
using the following equation:
        W —
                l +McV| —
                      i — McY«
   Report-the weight fraction VOC W0 as the
 arithmetic average of the three
 determinations.
   3.2  Volume Fraction VOC. Calculate the
 volume fraction volatile organic content V0
 using the following equation:
  4. Bibliography.
  4.1   Standard Test Method for Density of
Paint, Varnish, Lacquer, and Related
Products. ASTM Designation D 1475-60
(Reapproved 1980).
  4.2   Teleconversation. Wright, Chuck,
Inmont Corporation with Reich, R. A., Radian
Corporation. September 25,1979. Gravure Ink
Analysis.
  4.3   Teleconvexsation. Oppenheimer,
Robert, Gravure Research Institute with Burt,
Rick, Radian Corporation, November 5,1979.
Gravure Ink Analysis.
|PR Doc. B2-30410 Filed 11-B-81 *4B «n|
MLLING COOC •MO-fO-M
                                                               24A-5

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40 CFR Part 60, Appendix  A
Final, Promul gated
                    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, in some cases,
           an in-stack particulate filter is required.  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 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
           semi-continuous nonmethane organic (NMO) analyzer interfaced directly
           to the source may yield accurate results.  This approach has the
           advantage of providing emission data semi-continuously 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
                                        25-1

-------
detector responds predictably to the organic compounds in the stream.
If present, methane will, of course, also be measured.  In practice,
the FID can be applied to the determination of the mass concentration
of the total molecular structure of the organic emissions under 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 percentage of the
compounds is known or can be determined, and the FID response to the
compounds is known;  (4) where a consistent mixture of 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.
                             25-2

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     1.2  Principle.  An emission sample is withdrawn from the stack
at a constant rate through a chilled condensate trap by means  of an
evacuated sample tank.  TGNMO are determined by combining the
analytical results obtained from independent analyses of the condensate
trap and sample tank fractions.  After sampling is completed,  the
organic contents of the condensate trap are oxidized to carbon
dioxide (C02) which is quantitatively collected in an evacuated
vessel; then a portion of the COp is reduced to methane (CH,)  and
measured by a FID.  The organic content of the sample fraction
collected in the sampling tank is measured by injecting a portion into
a gas chromatographic (GC) column to achieve separation of the
nonmethane organics from carbon monoxide (CO), C02 and CH.; the
nonmethane organics (NMO) are oxidized to COg, reduced to CH^, and
measured by a FID.  In this manner, the variable response of the FID
associated with different types of organics is eliminated.
2.  Apparatus
     The sampling system consists of a condensate trap, flow control
system, and sample tank (Figure 1).  The analytical system consists
of two major sub-systems; an oxidation system for the recovery and
conditioning of the condensate trap contents and a NMO analyzer.  The
NMO analyzer is a GC with backflush capability for NMO analysis and
is equipped with an oxidation catalyst, reduction catalyst, and FID.
(Figures 2 and 3 are schematics of a typical NMO analyzer.)  The
system for the recovery and conditioning of the organics captured in
the condensate trap consists of a heat source, oxidation catalyst,
                             25-3

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nondispersive Infrared  (NDIR) analyzer and an  intermediate collection
vessel (Figure 4 is a schematic of a typical system.)  TGNMO
sampling equipment can  be constructed from commercially available
components and components fabricated in a machine shop.  NMO analyzers
are available commercially  or can be constructed from available
components by a qualified instrument laboratory.
      2.1  Sampling.  The following equipment is required:
      2.1.1   Probe.  3.2-mm  00  (1/8-in.) stainless steel tubing.
      2.1.2   Condensate  Trap.  Constructed of 316 stainless steel;
construction details of a suitable trap are shown in Figure 5.
      2.1.3   Flow Shut-off Valve.  Stainless steel control valve for
starting and stopping sample flow.
      2.1.4   Flow Control System.  Any system capable of maintaining
the  sampling rate  to within +_ 10 percent of the selected flow rate
(50  to 100 cc/min  range).
      2.1.5   Vacuum Gauge.   Gauge for monitoring the vacuum of the
sample tank  during leak checks and sampling.
      2.1.6   Sample Tank.  Stainless steel or aluminum tank with a
volume of 4  to 8 liters, equipped with a stainless steel  female quick
connect for  assembly to the sample train and analytical  system.
      2.1.7  Mercury Manometer.  U-tube mercury manometer  capable of
measuring pressure to within 1 mm Hg in the 0-900 mm range.
     2.1.8  Vacuum Pump.  Capable of evacuating to an absolute
pressure of  10 mm Hg.
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     2.2  Analysis.  The following equipment is required:
     2.2.1  Condensate Recovery and Conditioning Apparatus.   An
apparatus for recovering and catalytically oxidizing the condensate
trap contents is required.  Figure 4 is a schematic of such  a system.
The analyst must demonstrate prior to initial  use that the analytical
system is capable of proper oxidation and recovery, as specified in
section 5.1.  The condensate recovery and conditioning apparatus
consists of the following major components.
     2.2.1.1  Heat Source.  A heat source sufficient to heat the
condensate trap (including probe) to a temperature where the trap
turns a "dull red" color.  A system using both a propane torch and
an electric muffle-type furnace is recommended.
     2.2.1.2  Oxidation Catalyst.  A catalyst system capable of meeting
the catalyst efficiency criteria of this method (section 5.1.2).
Addendum I of this method lists a catalyst system found to be acceptable.
     2.2.1.3  Water Trap.  Any leak proof moisture trap capable of
removing moisture from the gas stream.
     2.2.1.4  NDIR Detector.  A detector capable of indicating CCL
concentration in the zero to 1 percent range.  This detector is required
for monitoring the progress of combustion of the organic compounds from
the condensate trap.
     2.2.1.5  Pressure Regulator.  Stainless steel needle valve
required to maintain the trap conditioning system at a near constant
pressure.
     2.2.1.6  Intermediate Collection Vessel.  Stainless steel or
aluminum collection vessel equipped with a female quick connect.
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Tanks with nominal volumes in the 1 to 4 liter range are
recommended.
     2.2.1.7  Mercury Manometer.  U-tube mercury manometer capable
of measuring pressure to within 1 mm Hg in the 0-900 mm range.
     2.2.1.8  Gas Purifiers.  Gas purification systems sufficient to
maintain C0« and organic impurities in the carrier gas and auxiliary
oxygen at a level of less than 10 ppm (may not be required depending
on quality of cylinder gases used).
     2.2.2  NMO Analyzer.  Semi-continuous GC/FID analyzer capable of:
 (1)  separating CO, CCL, and CH^ from nonmethane organic compounds, (2)
 reducing  the (XL  to CH. and quantifying as CH., and (3) oxidizing the
 nonmethane  organic compounds to CCL, reducing the CCL to CH. and
 quantifying as CH^.  The analyst must demonstrate prior to initial use
 that the  analyzer is capable of proper separation, oxidation, reduction,
 and  measurement (section 5.2).  The analyzer consists of the following
major components:
     2.2.2.1  Oxidation Catalyst.  A catalyst system capable of meeting
the  catalyst efficiency criteria of this method (section 5.2.1).
Addendum  I of this method lists a catalyst system found to be acceptable.
     2.2.2.2  Reduction Catalyst.  A catalyst system capable of meeting
the  catalyst efficiency criteria of this method (section 5.2.3).
Addendum I of this method lists a catalyst system found to be acceptable.
     2.2.2.3  Separation Column(s).  Gas chromatographic column(s)
capable of separating CO,  C02§  and CH4 from NMO compounds as demonstrated
according to the procedures established in this method (section 5.2.5).
Addendum I of this method  lists a column found to be acceptable.
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     2.2.2.4  Sample Injection System.   A GC sample injection  valve
fitted with a sample loop properly sized to interface with the NMO
analyzer (1 cc loop recommended).
     2.2.2.5  FID.  A FID meeting the following specifications is
required.
     2.2.2.5.1  Linearity.  A linear response (+_ 5J») over the  operating
range as demonstrated by the procedures established in section 5.2.2.
     2.2.2.5.2  Range.  Signal attenuators shall be available  to
produce a minimum signal response of 10 percent of full scale  for  a
full scale range of 10 to 50000 ppm CH4.
     2.2.2.6  Data Recording System.  Analog strip chart recorder
or digital integration system compatible with the FID for permanently
recording the analytical results.
     2.2.3  Barometer.  Mercury, aneroid, or other barometer capable
of measuring atmospheric pressure to within 1 mm Hg.
     2.2.4  Thermometer.  Capable of measuring the laboratory
temperature within 1°C.
     2.2.5  Vacuum Pump.  Capable of evacuating to an absolute pressure
of 10 mm Hg.
     2.2.6  Syringe(2).  10 yl and  100 ul  liquid injection syringes.
     2.2.7  Liquid Sample Injection Unit.  316 SS U-tube fitted with
a Teflon  injection septum, see Figure 6.
3.  Reagents
     3.1   Sampling.   Crushed  dry ice is  required during sampling.
     3.2   Analysis.
     3.2.1  NMO Analyzer.  The following  gases are needed:
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     3.2.1.1  Carrier Gas.  Zero grade gas containing less than
1 ppm C.  Addendum I of this method lists a carrier gas found to be
acceptable.
     3.2.1.2  Fuel Gas.  Pure hydrogen, containing less than 1  ppm C.
     3.2.1.3  Combustion Gas.  Zero grade air or oxygen as required
by the detector.
     3.2.2  Condensate Recovery and Conditioning Apparatus.
     3.2.2.1  Carrier Gas.  Five percent Og in N2, containing less
than 1 ppm C.
     3.2.2.2  Auxiliary Oxygen.  Zero grade oxygen containing less
than 1 ppm C.
     3.2.2.3  Hexane.  ACS grade, for liquid injection.
     3.2.2.4  Toluene.  ACS grade, for liquid injection.
     3.3  Calibration.  For all calibration gases, the manufacturer
must recommend a maximum shelf life for each cylinder (i.e., the
length of time the gas concentration is not expected to change more
Hian ^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.
     3.3.1  Oxidation Catalyst Efficiency Check Calibration Gas.   Gas
mixture standard with nominal concentration of 1  percent methane in air.
     3.3.2  Flame lonization Detector Linearity and Nonmethane  Organic
Calibration Gases (3).  Gas mixture standards with nominal  propane
concentrations of 20 ppm, 200 ppm, and 3000 ppm,  in air.
                             25-8

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     3.3.3  Carbon Dioxide Calibration Gases (3).  Gas mixture
standards with nominal C02 concentrations of 50 ppm, 500 ppm, and
1 percent, in air. Note:  total NMO less than 1 ppm required for
1 percent mixture.
     3.3.4  NMO Analyzer System Check Calibration Gases (4).
     3.3.4.1  Propane Mixture.  Gas mixture standard containing
(nominal) 50 ppm CO, 50 ppm CH4, 2 percent C02, and 20 ppm C3HQ,
prepared in air.
     3.3.4.2  Hexane.  Gas mixture standard containing (nominal)
50 ppm hexane in air.
     3.3.4.3  Toluene.  Gas mixture standard containing (nominal)
20 ppm toluene in air.
     3.3.4.4  Methanol.  Gas mixture standard containing (nominal)
100 ppm methanol in air.
4.  Procedure
     4.1  Sampling.
     4.1.1  Sample Tank Evacuation and Leak Check.  Either in the
laboratory or in the field, evacuate the sample tank to 10 mm Hg
absolute pressure or less (measured by a mercury U-tube manometer)
then leak check the sample tank by isolating the tank from the
vacuum pump and allowing the tank to sit for 10 minutes.   The tank
is acceptable if no change in tank vacuum is noted.
     4.1.2  Sample Train Assembly.  Just prior to assembly, measure
the tank vacuum using a mercury U-tube manometer.  Record  this vacuum
(pt-;)» the arcbient temperature (Tt1-), and the barometric pressure (Pbi)
at this time.  Assuring that the flow shut-off valve is in the closed
position, assemble the sampling system as shown in Figure  1.  Immerse
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the condensate trap body in dry ice to within 2.5 or 5  cm of the point
where the inlet tube joins  the trap body.
     4.1.3  Pretest Leak Check.  A pretest leak check is  required.
After the sampling train is assembled, record the tank  vacuum as
Indicated by the vacuum gauge.  Wait a minimum period of  10 minutes and
recheck the indicated vacuum.   If the vacuum has not changed, the
portion of the sampling train  behind the shut-off valve does not leak
and is considered acceptable.   To check the front portion of the
sampling train, assure that the probe tip  is tightly plugged and then
open the sample train flow  shut-off valve.  Allow the sample train  to
sit for a minimum period of 10 minutes.  The leak check is acceptable
if no visible change in the tank vacuum gauge occurs.  Record the
pretest leak rate (cm/Hg per 10 minutes).   At the completion of the
leak check period, close the sample flow shut-off valve.
     4.1.4  Sample Train Operation.   Place the probe into the stack such
that the probe 1s perpendicular to the direction of stack gas flow;
locate the probe tip at a single preselected point.  If a probe extension
which will not be analyzed  as  part of the  condensate trap is being  used,
assure that at least a 15 cm section of the probe which will  be analyzed
with the trap is in the stack  effluent.  For stacks having a negative
static pressure, assure that the sample port is sufficiently sealed to
prevent air in-leakage around  the probe.  Check the dry ice level and
add ice if necessary.  Record  the clock time and sample tank gauge
vacuum.  To begin sampling, open the flow  shut-off valve  and adjust (if
applicable) the control valve  of the flow  control system  used in the
sample train; maintain a constant flow rate (+_ 10 percent) throughout the
duration of the sampling period.  Record the gauge vacuum and flowmeter
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setting (if applicable) at 5-minute intervals.   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 due to reduced sample tank vacuum.  When the sampling is
completed, close the flow shut-off valve and record the final  sample
time and gauge vacuum readings.  Note:  If the 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 removing the probe from the stack,  remove  the
used sample tank from the sampling train (without disconnecting other
portions of the sampling train) and connect another sample tank to the
sampling train.  Prior to attaching the new tank to the sampling train,
assure that the tank vacuum (measured on-site by the U-tube manometer)
has been recorded on the data form and that the tank has  been  leak-
checked (on-site).  After the new tank is attached to the sample train,
proceed with the sampling until the required minimum sampling  time has
been exceeded.
     4.1.5  Post Test Leak Check.  A leak check is mandatory at the
conclusion of each test run.  After sampling is completed, remove  the
probe from the stack and plug the probe tip.  Open the sample  train
flow shut-off valve and monitor the sample tank vacuum gauge for a
period of 10 minutes.  The leak check is acceptable if no visible  change
in the tank vacuum gauge occurs.  Record the post test leak rate (cm Hg
per 10 minutes).   If the sampling train does not pass the post leak check,
invalidate the run or use a procedure acceptable to the Administrator to
adjust the data.

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     4.2  Sample Recovery.   After the post test leak check is
completed, disconnect the condensate trap at the flow metering system
and tightly seal both ends of the condensate trap.  Keep the trap packed
In dry ice until the samples are returned to the laboratory for analysis.
Remove the flow metering system from the sample tank.  Attach the
UVtube manometer to the tank (keep length of connecting line to a
minimum) and record the final tank vacuum (Pt); record the tank
temperature (Tt) and barometric pressure at this time.  Disconnect the
manometer from the tank.  Assure that the test run number is properly
identified on the condensate trap and the sample tank(s).
     4.3  Condensate Recovery and Conditioning.  Prepare the condensate
recovery and conditioning apparatus by setting the carrier gas flow rate
and heating the catalyst to its operating temperature.  Prior to initial
use of the condensate recovery and .conditioning apparatus, a system
performance test must be conducted according to the procedures
established in section 5.1  of this method.   After successful completion
of the initial performance test, the system is routinely used for sample
conditioning according to the following procedures:
     4.3.1  System Blank and Catalyst Efficiency Check.  Prior to and
iranedlately following the conditioning of each set of sample traps, or
on a daily basis (whichever occurs first) conduct the carrier gas blank
test ind catalyst efficiency test as specified in sections 5.1.1  and
5.T.2  of this method.  Record the carrier gas initial and final  blank
values, EL| and B.., respectively.  If the criteria of the tests  cannot
be met, make the necessary repairs to the system before proceeding.
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     4.3.2  Condensate Trap Carbon Dioxide Purge and  Sample Tank
Pressun'zation.  The first step in analysis is to purge the condensate
trap of any COp which it may contain and to simultaneously pressurize
the sample tank.  This is accomplished as follows:  Obtain both the
sample tank and condensate trap from the test run to  be analyzed.  Set
up the condensate recovery and conditioning apparatus so that the
carrier flow bypasses the condensate trap hook-up terminals,  bypasses
the oxidation catalyst, and is vented to the atmosphere.  Next, attach
the condensate trap to the apparatus and pack the trap in dry ice.
Assure that the valves isolating the collection vessel connection
from the atmospheric vent and the vacuum pump are closed and  then
attach the sample tank to the system as if it were the intermediate
collection vessel.  Record the tank vacuum on the laboratory  data
form.  Assure that the NDIR analyzerjindicates a zero output  level
and then switch the carrier flow through the condensate trap;
immediately switch the carrier flow from vent to collect.  The
condensate trap recovery and conditioning apparatus should now be
set up as indicated in Figure 8.  Monitor the NDIR; when C02 is no
longer being passed through the system, switch  the carrier flow
so that it once again bypasses the condensate trap.  Continue in
this manner until the gas  sample  tank  is  pressurized to a nominal
gauge pressure  of 800 mm Hg.  At  this  time,  isolate the tank, vent
the carrier flow, and record  the  sample tank pressure  (Ptf)»
barometric pressure  (Pbf)> and ambient temperature (Ttf).  Remove
the sample tank from  the system.
     4.3.3  Recovery  of  Condensate  Trap  Sample.  Oxidation and
collection of  the sample  in  the condensate  trap is new ready to begin.
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From the step just completed  in  section 4.3.1.2 above, the system
should be set up so that the  carrier flow bypasses the condensate
trap, bypasses the oxidation  catalyst,  and is vented to the atmosphere.
Attach an evacuated intermediate collection vessel to the system and
then switch  the carrier  so  that  it  flows through the oxidation
catalyst. Switch the carrier from  vent to collect and open the valve
to the collection vessel; remove the dry ice from the trap and then
switch the carrier flow  through  the trap.   The system should now be
set up to operate as indicated in Figure 9.  During oxidation of the
condensate trap sample,  monitor  the NDIR to determine when all the
sample has been removed  and oxidized (indicated by return to baseline
of NDIR analyzer output).   Begin heating the condensate trap and
probe with a propane torch.   The trap should be heated to a tempera-
ture at which the trap glows  a "dull red"  (approximately 500°C).
During the early part of the  trap "burn out," adjust the carrier and
auxiliary oxygen flow rates so that an  excess of oxygen is being fed
to the catalyst system.   Gradually  increase the flow of carrier gas
thrtHfgn the  trap.  After the  NDIR indicates that most of the organic
matter Was been purged,  place the trap  in  a muffle furnace (500°C).
Continue to  heat the probe  with  a torch or some other procedure
(e.g.i electrical resistance  heater).  Continue this procedure for at
least 5 minutes after the NDIR has  returned to baseline.  Remove the
heat from the trap but continue  the carrier flow until the
intermediate collection  vessel is pressurized to a gauge pressure of
800 mm Hg (nominal).  When  the vessel is pressurized, vent the carrier;
measure and  record the final  intermediate  collection vessel pressure
                              25-14

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(Pf) as well as the barometric pressure (Pby)» ambient temperature (T ),
and collection vessel volume (V ).
     4.4  Analysis.  Prior to putting the NMO analyzer into routine
operation, an initial performance test must be conducted.  Start the
analyzer and perform all the necessary functions in order to put the
analyzer in 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 determined, proceed with sample analysis
as follows:
     4.4.1  Daily operations and calibration checks.  Prior to and
immediately following 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 f'MC analyzer
performance test (section 5.2) before proceeding.
     4.4.2  Analysis of Recovered Condensate Sample.  Purge the sample
loop with sample and then inject a preliminary sample in order to
determine the appropriate FID attenuation.  Inject triplicate samples
from the intermediate collection vessel and record the values obtained
for the condensible organics as COg  (Ccm)-
     4.4.3  Analysis of Sample Tank.  Purge the sample loop with sample
and inject a preliminary sample in order to determine the appropriate
FID attenuation for monitoring the backflushed non-methane organics.
Inject triplicate samples from the sample tank and record the values
obtained for the nonmethane organics (C).
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5.  Calibration and Operational  Checks
     Maintain a record of performance of each item.
     5.1  Initial  Performance Check of Condensate Recovery and
Conditioning Apparatus.
     5.1.1   Carrier Gas and Auxiliary Oxygen Blank.  Set equal
flow rates  for both the carrier gas and auxiliary oxygen.  With the
trap switching valves in the bypass position and the catalyst in-line,
fill an evacuated  intermediate collection vessel with carrier gas.
Analyze the collection vessel  for C02; the carrier blank is acceptable
if the C0~  concentration is less than 10 ppm.
     5.1.2   Catalyst Efficiency  Check.  Set up the condensate trap
recovery system so that the carrier flow bypasses the trap inlet and
is vented to the atmosphere at the system outlet.  Assure that the
valves Isolating the collection  system from the atmospheric vent
and vacuum  pump are closed  and then attach an evacuated intermediate
collection  vessel  to the system.   Connect the methane standard gas
cylinder (section  3.3.1) to the  system's condensate trap connector
(probe end, Figure 4).   Adjust the system valving so that the standard
gas cylinder acts  as the carrier gas and adjust the flow rate to the
rate normally used during trap sample recovery.  Switch off the
auxiliary oxygen flow and then switch from vent to collect in order to
begin collecting a sample.   Continue collecting a sample.in a normal
manner until the intermediate vessel is filled to a nominal gauge
pressure of 300 ram Hg.  Remove the intermediate vessel from the system
and vent the carrier flow to the atmosphere.  Switch the valving to return
the system to its  normal carrier gas and normal operating conditions.
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Analyze the collection vessel for C02; the catalyst efficiency is
acceptable if the C02 concentration is within +_ 5 percent of the
expected value.
     5.1.3  System Performance Check.  Construct a liquid sample
injection unit similar in design to the unit shown in Figure 6.   Insert
this unit into the condensate recovery and conditioning system in  place
of a condensate trap and set the carrier gas and auxiliary oxygen
flow rates to normal operating levels.  Attach an evacuated
intermediate collection vessel 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 5.1.3.1 to 5.1.3.4) via the injection septum.  Heat the injection
unit with a torch while monitoring the oxidation reaction on the NOIR.
Continue the purge until the reaction is complete.  Measure the final
collection vessel 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 j^lO percent with a relative  standard deviation (section 6.7)
of less than 5 percent  for each  set  of triplicate  injections as
follows:
     5.1.3.1   100 ul  hexane.
     5.1.3.2   10 yl  hexane.
     5.1.3.3   100 yl  toluene.
     5.1.3.4   10 yl  toluene.
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     5.2  Initial  NMO Analyzer  Performance Test.
     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 3.3.1).
The oxidation catalyst operation is acceptable if no FID response
is noted.
     5.2.2  Analyzer Linearity  Check and NMO Calibration.  Operating
both the oxidation and reduction catalysts, conduct a linearity check
of the analyzer using the propane  standards specified in section 3.3.
Make triplicate Injections of each calibration gas and then calculate
the avenge 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 + 5  percent of the overall mean value and if the
relative standard  deviation (section 6.7) for each set of triplicate
injections is less than  +_ 5 percent.  Record the overall mean of the
propane response factor  values  as the NMO calibration response factor
      5.2.3  Reduction Catalyst Efficiency Check and C02 Calibration.
 An exact determination of the reduction catalyst efficiency is not
 required.  Instead, proper catalyst operation is indirectly checked and
 continuously monitored by establishing a CO  response factor and comparing
 it to the NMO response factor. Operating both the oxidation and reduction
 catalysts make triplicate injections of each of the C02 calibration
 gases (section 3.3.3).  Calculate the average response factor  (area/
 pom) for each calibration gas, as well as the overall mean of  the
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response factor values.  The reduction catalyst operation  is  accept-
able if the average response factor of each calibration  gas  is  within
+_ 5 percent of the overall mean value and if the relative  standard
deviation (section 6.7) for each set of triplicate injections is  less
than +_5 percent.  Additionally, the CCL overall mean response factor
must be within +_ 10 percent of the NMO calibration response  factor
(RFNMO) calculated in section 5.2.2.  Record the overall mean of  the
response factor values as the CC^ calibration response factor
-
     5.2.4  NMO System Blank.  For the high level C02 calibration gas
(section 3.3.3) record the NMO value measured during the C02 calibration
conducted in section 5.2.3.  This value is the NMC blank value for the
analyzer (B_) and should be less than 10 ppm.
           a
     5.2.5  System Performance Check.  Check the column separation
and overall performance of the analyzer by making triplicate injections
of the calibration gases listed  in section 3.3.4.  The analyzer
performance is acceptable  if the measured NMO value  for each
gas (average of triplicate  injections)  is within +J2 percent of
the expected value.
     5.3  NMO Analyzer Daily Calibration.
     5.3.1  NMO  Blank  and  C02>   Inject  triplicate samples of the high
level  C02 calibration  gas  (section  3.3.3)  and  calculate the average
response factor.   The  system operation  is  adequate  if the calculated
response factor  is within  +_ 10  percent  of  the  RFCQ   calculated during
the initial  performance  test  (section 5.2.2).   Use  the daily  response
factor (DRFrn  )  for  analyzer  calibration and the calculation  of
                              25-T9

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measured C0? concentrations in the collection vessel samples.
In addition, record the NMO blank value (Ba); this value should
                                          a
be less than 10 ppm.
     5.3.2  NMO Calibration.  Inject triplicate samples of the
mixed propane calibration cylinder (section 3.3.4.1) and calculate
the average NMO response factor.  The system operation is adequate
if the calculated response factor is within +^10 percent of the
RF^ calculated during the initial performance test (section 5.2.1).
Use the dally response factor (DRFMMn) for analyzer calibration and
                                  IMPi\/
calculation of NMO concentrations in the sample tanks.
     5.4  Sample Tank.   The volume of the gas sampling tanks used
must be determined.  Prior to putting each tank in service, determine
the tank volume by weighing the tanks empty and then filled with
de1on1zed distilled water; weigh to the nearest 5 gm and record the
results.  Alternatively, measure the  volume of water used to fill
the tanks to the nearest 5 ml.
     5.5  Intermediate  Collection Vessel.   The volume of the
intermediate collection vessels  used  to collect C0« during the analysis
of the condensate traps must be  determined.   Prior to putting each
vessel into service, determine  the volume  by weighing the vessel
enpiy afid then filled with deionized  distilled water;  weigh to the
nearest 5 gm and record the results.   Alternatively,  measure the
volume of water used to fill  the tanks to  the nearest 5 ml.
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6.  Calculations
     Note:  All equations are written using absolute pressure;
absolute pressures are determined by adding the measured barometric
pressure to the measured gauge pressure.
     6.1  Sample Volume.  For each test run, calculate the gas
volume sampled:
          V   = 0.386 V  *•
           s            V Tt    t
     6.2  Noncondensible Orgam'cs.  For each sample tank, determine
the concentration of nonmethane organics (ppm C):
                  tf
               Tt " Tt1
                            F
     6.3  Condensible Organics.  For each condensate trap determine
the concentration of organics  (ppm C):
Vv Pf
C = 0.386 T^UJ-
s f
1 q
q k^ cmk ' t
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     6.4  Total  Gaseous  Nonmethane Orgam'cs (TGNMO).  To determine
the TGNMO concentration  for each test run, use the following
equation:
          c =  ct + cc
     6.5  Total  Gaseous Nonmethane Orgam'cs (TGNMO) Mass
Concentration.   To determine the TGNMO mass concentration as
carbon for each  test run,  use the following equation:
          Mc * 0.498 C
     6.6  Percent Recovery.   To calculate the percent recovery for
the liquid injections to the condensate recovery and conditioning
system use the following equation:
          percent recovery = 1.6  -r-  —•
                                  L  p
     6.7  Relative Standard Deviation,

                100
          RSO
                           n - 1
                             25-22

-------
Where:  B    -  Measured NMO blank value for NMO analyzer,  ppm C
         a
        EL    = Measured C02 blank value for condensate recovery
                and conditioning system carrier gas,  ppm C02.
        C    =  Total gaseous nonmethane organic (TGNMO) concentration
                of the effluent, ppm C equivalent.
        C    s  Calculated condensible organic (condensate  trap)
                concentration of the effluent, ppm C  equivalent.
        C    =  Measured concentration (NMO analyzer) for the
                condensate trap (intermediate collection vessel),
                ppm C02.
        Ct   =  Calculated noncondensible organic concentration
                (sample tank) of the effluent, ppm C  equivalent.
        C.   «  Measured concentration (NMO analyzer) for the
         tm
                sample tank, ppm NMO.
        L    =  Volume of liquid injected, microliters.
        M    =  Molecular weight of the liquid injected, g/g-mole.
        M    =  Total gaseous non-methane organic (TGNMO) mass
                concentration of the effluent, mg C/dscm.
        N    *  Carbon number of the liquid compound injected
                (N = 7 for toluene, N ~ 6 for  hexane).
        Pf   =  Final pressure of the intermediate collection vessel,
                mm Hg absolute.
        P..  =  Gas  sample tank pressure  prior to sampling, mm Hg
                absolute.
                             25-23

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P.   =  Gas sample tank pressure after sampling,  but prior
        to pressurizing, mm Hg absolute.
P -  »  Final  gas sample tank pressure after pressurizing,
        mm Hg  absolute.
Tf   -  Final  temperature of intermediate collection vessel,
        °K.
Tt4  -  Sample tank temperature prior to  sampling,  °K.
Tt   ~  Sample tank temperature at completion of  sampling, °K.
Ttx  s  Sample tank temperature after pressurizing, °K.
V    =  Sample tank volume, cm.
V    =  Intermediate collection vessel volume, cm.
V    *  Gas volume sampled, dscm.
n    =  Number of data  points.
q    *  Total  number of analyzer injections of intermediate
        collection vessel during analysis (where  k  = injection
        number, 1 .  . q).
r    s  Total  number of analyzer injections of sample tank
        during analysis (where j = injection number,
        1 . .  .r).
Xj   *  Individual measurements.
IT   «  Mean value.
p    s  Density of liquid injected, g/cc.
                     25-24

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7.  Bibliography
     7.1  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,  MA.  June 15-20,  1975.)  14 p,
     7.2  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, CO.
June 9-13, 1974.)  25 p.
                             25-25

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                            METHOD  25
                  ADDENDUM  I.   SYSTEM COMPONENTS
     In test Method 25  several  important system components are
not specified;  instead  minimum  performance specifications are
provided.   The  method is written  in  this manner to permit individual
preference in choosing  components, as well as, to encourage
development and use of  improved components.  This addendum is added
to the method in order  to provide users with some specific information
regarding  components which  have been found satisfactory for use with
the method.  This listing is given only for the purpose of providing
information and does not constitute  an  endorsement of any product by
the Environmental Protection Agency. This list is not meant to imply
that other components not listed  are not acceptable.
     1. Condensate Recovery and  Conditioning System Oxidation Catalyst.
3/8" OD X  14" inconel tubing packed  with 8 inches of hopcalite*
oxidizing  catalyst and  operated at 800°C in a tube furnace.  Note: A
this temperature, this  catalyst must be purged with carrier gas at
all times  to prevent catalyst  damage.
     2.  NMO Analyzer Oxidation Catalyst.  1/4" OD X 14" inconel
tubing packed with 6 inches of hopcalite oxidizing catalyst and
operated at 800°C in a  tube furnace.  (See note above.)
     3.  NMO Analyzer Reduction Catalyst.  Reduction Catalyst Module;
Byron  Instruments, Raleigh, N.C.
   MSA registered trade mark.
                               25-26

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     4.  Gas Chromatographic Separation Column.   1/8 inch OD
stainless steel packed with 3 feet of 10 percent methyl  silicone,
Sp 2100 (or equivalent) on Supelcoport (or equivalent),  80/100
mesh, followed by 1.5 feet Porapak Q (or equivalent) 60/80 mesh.
The inlet side is to the silicone.  Condition the column for
24 hours at 200°C with 20 cc/min N« purge.
     During analysis for the nonmethane organics the separation
column is operated as follows:  First, operate the column at -78°C
(dry ice bath) to elute CO and CH4.  After the CH4 peak
operate the column at 0°C to elute C02-  When the C02
is completely eluted, switch the carrier flow to backflush the
column and simultaneously raise the column temperature to 100° C  in
order to elute all nonmethane organics (exact timings for column
operation are determined from the calibration standard).
     Note:  The dry ice operating condition may be deleted if
separation of CO and CH^ is unimportant.
     Note:  Ethane and ethylene may or may not be measured using
this column; whether or not ethane and ethylene are quantified
will depend on the C02 concentration in the gas sample.  When high
levels of C02 are present, ethane and ethylene will elute under
the tail of the C02 peak.
     5.  Carrier Gas.  Zero grade nitrogen or helium or zero air.
                              25-27

-------
   PROBE
 EXTENSION
(IF REQUIRED)
                                                                     VACUUM
                                                                     GAUGE
                  FLOW
                  RATE
               CONTROLLER
          STACK
          WALL

           11
                           PROBE
mv ICE
AREA


u




        VALVE
CONNECTOR
 QUICK  pi
CONNECTO
                           A
                                   CONOENSATE
                                     TRAP
                          EVACUATED
                           SAMPLE
                            TANK
                       Figure 1. Sampling apparatus.
                                 25-28

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                              CARRIER GAS
 CALIBRATION STANDARDS
          SAMPLE TANK
         INTERMEDIATE
          COLLECTION
            VESSEL
    (CONDITIONED TRAP SAMPLE)
                                           BACKFLUSH
                                            NON-METHANE
                                             OR6ANICS
                                                      HYDROGEN
                                                      COMBUSTION
                                                          AIR
Figure 2.  Simplified schematic of non-methane organic (NMO) analyzer.
                           25-29

-------
     ZERO
      AIR
      OR
    5 percent
     02/N2
            VALVE
en
i
           FLOW
         REGULATOR
                        FLOW
                       METER
CATALYST
 BYPASS
  VENT
                        '/CATALYST
                         BYPASS VALVE
                           OXIDATION
                           CATALYST
             I
             I
HEATED       I
CHAMBER     j
                           CATALYST
                            BYPASS
       VENT
                             CATALYS1
                              BYPASS
                              VALVE
                           REDUCTION
                           CATALYST
                     |   HEATED CHAMBER
                     |	\
                                              f
                                 SEPARATION
                                   COLUMN

                       NONMETHANE
                         ORGANIC
                       (BACKFLUSH)
CO
C02
CH4
                             COLUMN
                           BACKFLUJ
                             VALVE
                     f*\ VALVt
                                               AIR
                                                                        INJECT
                                                                        VALVE
                                              SAMPLE / CALIBRATION
                                              TANK /  CYLINDERS
                                                   MOLECULAR
                                                     SIEVE
                                           GAS
                                       PURIFICATION
                                         FURNACE
                                                                                                                        FLOW
                                                                                                                       METER
                                        Figure 3. Nonmethane organic (NMO) analyzer.

-------
                    FLOW
                  .CONTROL
                 1  VALVES
                                                            SAMPLE
                                                          CONOENSATE
                                                             TRAP
     CARRIER
     '5 percent
      02/N2
                                                               OXIDATION
                                                               CATALYST

                                               VENT   HEAT
                                                            NOIR
                                                          ANALYZER
                        REGULATING
                          VALVE
                                    •  FOR MONITORING PROGRESS
                                        OF COMBUSTION ONLY
                            QUICK
                           CONNECT
VACUUM**
  PUMP
                                                                                 H20
                                                                                 TRAP
 MERCURY
MANOMETER
INTERMEDIATE
 COLLECTION
   VESSEL
"FOR EVACUATING COLLECTION
  VESSELS AND SAMPLE TANKS
         (OPTIONAL)
                   Figure 4.   Condensate recovery and conditioning apparatus.
                                             25-31

-------
                                                       PROBE, 3mm (1/8 in) 0.0.

                              INLET TUBE, 6mm (% in) 0.0.          V
           CONNECTOR
EXIT TUBE, 6mm (V. in) O.D.
                                                                   CONNECTOR
                                          CONNECTOR/REDUCER
    NO. 40 HOLE
(THRU BOTH WALLS)
       WELDED JOINTS
                                         CRIMPED AND WELDED GAS-TIGHT SEAL
                                      ^BARREL 19mm (>/. in) 0.0. X 140mm (S-% in) LONG,
                                                 1.5mm (1/16 in) WALL
                                       BARREL PACKING. 316 SS WOOL PACKED TIGHTLY
                                               AT BOTTOM, LOOSELY AT TOP
                                        HEAT SINK (NUT, PRESS-FIT TO BARREL)
                                      WELDED PLUG
               MATERIAL: TYPE 316 STAINLESS STEEL

                          Figure 5. Condensate trap^.

                                       25-32

-------
                                INJECTION
                                SEPTUM
FROM
CARRIER
        CONNECTING T
               >—1
               APPRO X.
             15 cm (6 in)
                                               CONNECTING
                                               ELBOW
                                                                TO
                                                                CATALYST
                                                    'S
                                                      6 mm (1/4 in)
                                                      316 SS TUBING
                 Figure 6.  Liquid sample injection unit.
                                    25-33

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                                   VOLATILE ORGANIC CARBON
FACILITY.
LOCATION.
DATE	
              SAMPLE LOCATION.
              OPERATOR	
              RUN NUMBER.
TANK NUMBER.
 .TRAP NUMBER.
.SAMPLE ID NUMBER.
TANK VACUUM,
mm Hj cm Hg
PRETEST (MANOMETER)
POST TEST (MANOMETER)




(RAUGP1
(GAUGE)

BAROMETRIC
PRESSURE.
mm Hg



AMBIENT
TEMPERATURE,
°C



LEAK RATE
cm H| / 10 mm

TIME
CLOCK/SAMPLE


















PUCTFCT
MSTTfST
GAUGE VACUUM,
em H«


















FLOWMETER SETTING



















COMMENTS


















                                Figure 7. Example Field Data Form.
                                              25-34

-------
\
J 	 '•' •
FLOW
X METERS \ ! yJL

T 7 -^ FLOW |
(1 1 <=*/ CJJ ,T5p c \ <^ H SWITCHING
a n t>5 cS i— i M VALVES M "

(OPEN) (OPEN) CONNECTORS
/ \

PURIFIER ,-!-_ p1-!
_ |r-ii ir~ii

HX^ V
I 1 1 	 	
CARRIFR SAMPLE 1 ,
CATALYST
BYPASS
VENT
l-WAY ^.^
ALVES-^ j
02 15 percent CONDENSATE' | OXIDATION '
02/N2 | TRAP | CATALYST '
1 H
U DRY ICE 1 Cj.
VENT
f
,*\ NOIR "*
J-, L ^
(OPEN) V— 0 REGULATING V_JS • FOR MONITORING PROGRESS
/\ VALVE £\ V OF COMBUSTION ONLY
1 (OPEN) 1
QUICK [J-i
1 CONNECT IQ
ICLOSED)V-|) I f~~^\
A^XA ^ J) "FOR EVACUATING COLLECTION
VACUUM" '<^/ iMTCDMcniflTF VbSSbLS AND SAMPLb 1 ANKS
OMMO MCQPIIQV INTERMED Alt
PUMP MERCURY rniiFrruiN (OPTIONAL)
MANOMETER COLLECTION
VESSEL
EATEO |
(AMBER ,

1
i
1
\y
H20
TRAP
Figure  8.  Condensate recovery  and conditioning apparatus,  carbon dioxide purge.
                                       25-35

-------
                 (OPEN)
(CLOSED) V—{)
REGULATING
   VALVE
   (OPEN)

   QUICK
  CONNECT
VACUUM"
  PUMP
                                                       FOR MONITORING PROGRESS
                                                         OF COMBUSTION ONLY
                                                          H20
                                                          TRAP
                     MERCURY
                    MANOMETER
      COLLECTION
        VESSEL
                               "FOR EVACUATING COLLECTION
                                VESSELS AND SAMPLE TANKS
                                        (OPTIONAL)
           Figure 9.  Condensate recovery and conditioning apparatus,  collection of trap organics.
                                                  25-36

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Federal Register /  Vol. 45, No. 194 / Friday, October 3. 1980  /  Rulei and Regulation*
    Method 25—Detoratnalioii of Total Gaaeoue
    Nonmethane Organic EndMkm u Carbon
    I. Applicability and Principle
      1.1  Applicability. Thii method applies to
    the measurement of volatile organic
    compounds (VOC) aa total gaseous
    nonmethane organic* (TGNMO) aa carbon in
    louroa emission*. Organic paniculate natter
    will Interfere with the analytic and therefore.
    in aome cases, an to-etack partieulate filter ia
    required. This method it not the only method
    thai applies to the neeaureiMot of TGNMO.
Colts, logistics, and other practicalities of
source testing may make other test methods
more desinble (or measuring VOC of certain
effluent streams. Proper judgment it lequired
in determining the moat applicable VOC teat
method. For example, depending upon the
molecular weight of the organic! in the
effluent stream,  a totally automated semi-
continuous nonmethane organic (NMO)
analyzer interfaced directly to the source
may yield accurate results. This approach hat
the advantage of providing emission data
•emi-continuously over an extended time
period.
  Direct measurement of an effluent with a
flame tonization 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
will, of course, also be measured. In practice,
the FID can be applied to the determination
of the maaa concentration of the total
molecular structure of the organic emissions
under 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 percentage of the compounds in
known or can be determined, and the FID
response to the  compound* is known: (4)
where a consistent mixture of compounds
exists before and after emission control and
only the relative concentrations are to bf
aaaeaaed; or (5)  where the FID can be
calibrated against mass standards of the
compounds emitted (aolvent emissions, for
example).
  Another example of the use of a direct FID
la aa a screening method. If there is enough
information available to provide a rough
estimate of the  analyser accuracy, flic FID
analyzer can be used to determine the VOC
content of an unchancterixed gaa 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.
   to situations where a Qualitative/
quantitative analysis of an effluent stream ia
desired or required, a gas chrometographic
FID system may apply. However, for scum's
emitting  numerous organic*, the time and
expense  of this  approach  will be formidable
   1.2  Principle. An emission sample is
withdrawn from the stack at a constant rate
through a chilled oondenaate trap by means
of an evacuated sample tank. TGNMO air
determined by combining the analytical
results obtained from independent analyse*
of the condensate trap and sample tank
 fractions. After sampling is completed, the
 organic contents of the condensate trap  are
oxidized to carbon dioxide (CO,) which  is
 quantitatively collected in an evacuated
 vessel; then a portion of the COt is reduced to
 methane (CK)  and measured by a FID The
 organic content of the sample fraction
 collected in the sampling tank is measured by
 injecting a portion into a gas
 chromatographic (GC) column to achieve
 separation of the nonmethane organics from
 carbon monoxide (CO), CO, and CH.; the
 nonmethane organics (NMO) are oxidized to
                                               25-37

-------
 Federal Register / Vol. 45. No. 194  / Friday.  October 3.  1980  /  Rules and Regulations
	-^———^—^—^—^—• "i ii.     ^^^^
CO* reduced to CH* and measured by a FID.
In this manner, the variable response of the
FID associated with different types of
organics is eliminated.

2. Apparatus
  The sampling system consist* of a
condensate trap, flow control system, and
sample tank (Figure 1). The analytical system
consists of two major sub-systems: an
oxidation system for the recovery and
conditioning of the condensate trap contents
and a NMO analyzer. The NMO analyzer is a
CC with backflush capability for NMO
analysis and is equipped with an oxidation
catalyst reduction catalyst and FID. (Figures
2 and 3 an schematics of a typical NMO
analyzer.) The system for the recovery and
conditioning of the organics captured in the
condensate trap consists of a heat source,
oxidation catalyst nondlspenive infrared
(NDOt) analyzer and an intermediate
collection vessel (Figure 4 is a schematic of a
typical system.) TGNMO sampling equipment
can be constructed from commercially
 available components and components
 fabricated in a machine shop. NMO
 analyzers are available commercially or can
 be constructed from available components by
  a qualified instrument laboratory.
   2.1  Sampling. The following equipment is
  required:
   2.1.1  Probe. 3.2-mm OD (*4a.) stainless
  steel tubing.
   2.1.2  Condensate Trap. Constructed of 316
  stainless steel; construction details of a
  suitable trap an shown in Figure 5,
    2.1.3  Flow Shut-off Valve. Stainless steel
  control valve for starting and stopping
  sample flow.
    2.1.4  Flow Control System. Any system
  capable of maintaining the sampling rate to
  within ±10 percent of the selected flow rate
  (SO to 100 cc/min range).
    2.1.5 Vacuum Gauge. Gauge tor
  monitoring the vacuum of the sample tank
  during teak checks and sampling.
    2.1.6 Sample Tank. Stainless steel or
  aluminum tank with a volume of 4 to 8 liters,
  equipped with a stainless steel female quick
  connect for assembly to the sample train and
  analytical system.
    2.1.7 Mercury Manometer. U-tube
  mercury manometer capable of measuring
  pressure to within 1 mm Hg In the 0-000 mm
  range.
    2.1.8 Vacuum Pump. Capable of
  evacuating to an absolute pressure of 10 mm
  Hg.
    12  Analysis. The following equipment is
  required:
    2.2.1 Condensate Recovery and
  Conditioning Apparatus. An apparatus for
  recovering and catalytically oxidizing the
  condensate trap contents is required. Figure 4
  is a schematic of such a system. The analyst
  must demonstrate prior to initial use that the
  analytical system is capable of proper
  oxidation and recovery, as specified in
  section 5.1. The condensate recovery and
  conditioning apparatus consists of the
  following major components.
    2X1.1  Heat Source. A heat source
  sufficient to heat the condensate trap
  (including probe) to a temperature where the
   trap turns a "dull red" color. A system using
                              both a propane torch and an electric muffle-
                              type furnace is recommended.
                                2.2.1.2  Oxidation Catalyst A catalyst
                              system capable of meeting the catalyst
                              efficiency criteria of this method (section
                              5.1.2). Addendum I of this method lists a
                              catalyst system found to be acceptable.
                                2.2.1.3  Water Trap. Any leak-proof
                              moisture trap capable of removing moisture
                              from the gas stream.
                                2.2.1.4  NDIR Detector. A detector capable
                              of indicating CO. concentration in the zero to
                              1 percent range. This detector is required for
                              monitoring the progress of combustion of the
                              organic compounds from the condensate trap.
                                 2.2.1.5  Pressure Regulator. Stainless steel
                               needle valve required to maintain the trap
                               conditioning system at a near constant
                               pressure.
                                 2X1.6  Intermediate Collection Vessel
                               Stainless steel or aluminum collection vessel
                               equipped with a female quick connect Tanks
                               with nominal volumes in the 1 to 4 liter range
                               are recommended.
                                 2X1.7  Mercury Manometer. U-tube
                               mercury manometer capable of measuring
                               pressure to within 1 mm Hg in the 0-900 mm
                               range.
                                 2X1.8 Gas Purifiers. Gas purification
                               systems sufficient to maintain CO, and
                               organic impurities in the carrier gas and
                               auxiliary oxygen at a level of leas than 10
                               ppm (may not be required depending on
                               quality of cylinder gases used).
                                 2X2  NMO Analyzer. Semi-continuous
                               CC/FID analyzer capable ofc (1) separating
                               CO. CO» and CH. from nonmetfaane organic
                               compounds. (2) reducing the CO, to CH. and
                               quantifying as CH. and (3) oxidizing the
                               nonmethane organic con-xmnda to CO»
                               reducing the COi to CH. and quantifying as
                               CH* The analyst must demonstrate prior to
                                initial use that the analyzer is capable of
                                proper separation, oxidation, reduction, and
                                measurement (section U). The analyzer
                                consists of the fallowing major components:
                                  2X2.1  Oxidation Catalyst A catalyst
                                system capable of meeting the catalyst
                                efficiency criteria of this method (section
                                5X1). Addendum I of this method lists a
                                catalyst system found to be acceptable.
                                  2-2-*-*  Reduction Catalyst A catalyst
                                system capable of meeting the catalyst
                                efficiency criteria of this method (section
                                5X3). Addendum I of thi* method lists s
                                catalyst system found to be acceptable.
                                  2.2.2.3  Separation Column(s). Gas
                                chromatographic columnfs) capable of
                                separating CO. CO* and CH. from NMO
                                compounds as demonstrated according to the
                                procedures established in this method
                                (section SOS). Addendum 1 of this method
                                lists a column found to be acceptable.
                                  2X2.4  Sample Injection System. A GC
                                sample injection valve fitted with a sample
                                loop properly sized to interface with the
                                NMO analyzer (1 cc loop recommended).
                                   8.8.2.*-   FOX A FID meeting the following
                                specifications is required.
                                   2.225.1  Linearity. A linear response (±
                                5%) over the operating range as demonstrated
                                by the procedures established in section 5X2.
                                   2.28S8  Range. Signal attenuators shall
                                 be available to produce a minimum signal
                                 response of 10 percent of full scale for a full
                                 scale range of 10 to 50000 ppm OU
  2X2.0  Data Recording System. Analog
Strip chart recorder or digital intergration
system compatible with the FID for
permanently recording the analytical results.
  2,2,?  Barometer. Mercury, aneroid, or
other barometer capable of measuring
atmospheric pressure to within 1 ram Hg.
  2X4  Thermometer. Capable of measuring
the laboratory temperature within 1'C.
  2.2.5  Vacuum Pump. Capable of
evacuating to an absolute pressure of 10 mm
Hg.
  2X6  Syringe (2). 10 ul and 100 pi liquid
injection syringes.
  2X7  Liquid Sample Injection Unit 318 SS
U-tube fitted with a Teflon injection septum.
see Figure ft.

3. Reagents
  3.1  Sampling. Crushed dry ice is required
during sampling.
  3.2  Analysis.
  3X1   NMO Analyzer. The following gases
are needed:
  3X1.1 Carrier Gas. Zero grade gas
containing less than 1 ppm C Addendum I of
 this method lists a carrier gas found to be
 acceptable.
   3X12 Fuel Gas. Pure hydrogen.
 containing less than 1 ppm C
   3X1.3 Combustion Gas. Zero grade air or
 oxygen as required by the detector.
   3X2  Condensate Recovery and
 Conditioning Apparatus.
   3X2.1  Carrier Gas. Five percent O* in N»
 containing less than 1 ppm C.
   3.2X2 Auxiliary Oxygen. Zero grade
 oxygen containing less than 1 ppm C
   3XX3 Hexane. ACS grade, for liquid
 injection.
   3X2.4 Toluene. ACS grade, for liquid
 injection.
    3.3  Calibration. For all calibration gases.
 the manufacturer must recommend a
           shelf life for each cylinder (i.e., the
  UMUMUieue* BBBMBMSI a**w «»» »•"••» •—f~~™™r"•* — \	*
  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.
    3X1  Oxidation Catalyst Efficiency Check
  Calibration Gas. Gas mixture standard with
  nominal concentration of 1 percent methane
  in air.
    3X2 Flame lonization Detector Linearity
  and Nonmethane Organic Calibration Gases
  (3). Gas mixture standards with nominal
  propane concentrations of 20 ppm. 200 ppm.
  and 3000 ppm. in air.
    3.34 Carbon Dioxide Calibration Gases
  (3). Gas mixture standards with nominal COi
  concentrations of 50 ppm. 500 ppm, and 1
  percent in air. Note: total NMO less than 1
  ppm required for 1 percent mixture.
    3X4 NMO Analyzer System Check
  Calibration Gases (4).
    3X4.1  Propane Mixture. Gas mixture
  standard containing (nominal) 50 ppm CO, 50
  ppm CH* 2 percent CO* and 20 ppm CJi*
  prepared in air.
    3.3.4.2  Hexane. Gas mixture standard
  containing (nominal) 50 ppm hexane in air.
                                              25-38

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              Federal Register /  Vol. 45,  No.  194  / Friday. October  3.  1980  / Rules and  Regulations
  3.3.4.3  Toluene. Gas mixture standard
containing (nominal) 20 ppm toluene in air.
  3.3.4.4  Mefhanol. Gas mixture standard
containing (nominal) 100 ppm methane! in air.

4. Procedure
  4.1  Sampling.
  4.1.1  Sample Tank Evacuation and Leak
Check. Either in the laboratory or in the field.
evacuate the sample tank to 10 nun Hg
absolute pressure or less (measured by a
mercury U-tube manometer) then leak check
the sample tank by isolating the tank  from
the vacuum pump and allowing the tank to sil
for 10 minutes. The tank is acceptable if no
change in tank vacuum is noted.
  4.1.2  Sample Train Assembly. Just prior to
assembly, measure the tank vaccuum using a
mercury U-tube manometer. Record this
vaccum (Pu), the ambient temperature (Tu),
and the barometric pressure (P»J at this time.
Assuring that the flow shut-off valve is in the
closed position, assemble the sampling
system as shown in Figure 1. Immerse the
condensate trap body in dry ice to within 2.5
or 5 cm of the point where the inlet tube joins
the trap body.
  4.1.3.  Pretest Leak Check.  A pretest leak
check is required. After the sampling  train is
assembled, record the tank vacuum as
indicated by the vaccum gauge. Watt a
minimum period of 10 minutes and recheck
the indicated vacuum. If the vacuum has not
changed the portion of the sampling train
behind the shut-off valve does not leak and is
considered acceptable. To check the front
portion of the sampling train,  assure that the
probe tip is tightly plugged and then open the
sample train flow shut-off valve. Allow the
sample train to sit for a minimum period of 10
minutes. Hie leak check is acceptable if no
visible change  in the tank vacuum gauge
occurs. Record the pretest leak rate (cm/Hg
per 10 minutes). At the completion of the leak
check period, dose the sample flow shut-off
valve.
  4.1.4.  Sample Train Operation. Place  the
probe into the stack  such that the probe is
perpendicular to the direction of stack gas
flow; locate the probe tip at a single
preselected point If a probe extension which
will not be analyzed as part of the
condensate trap is being used, assure that at
least a IS cm section of the probe which will
be analyzed with the trap is in the stack
effluent For stacks having a negative static
pressure, assure that the sample port is
sufficiently sealed to prevent air in-leakage
around the probe. Check the dry ice level and
add ice If necessary. Record the dock time
and sample tank gauge vacuum. To begin
sampling, open the flow shut-off valve and
adjust (if applicable) the control valve of the
How control system used in the sample train:
maintain a constant flow rate (±10 percent)
throughout the duration of the sampling
period. Record the gauge vacuum and
flowmeter setting (if applicable) at 5-minute
intervals. 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 due to
reduced sample tank vacuum. When the
sampling is completed, close the flow shut-off
valve and record the final sample time and
guage vacuum readings. Note: If the 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 removing the probe from the
stack, remove the used sample tank from the
sampling train (without disconnecting other
portions of the sampling train) and connect
another sample  tank to the sampling train
Prior to attaching the new tank  to the
sampling train, assure that the tank vacuum
(measured on-site by the U-tube manometer)
has been recorded on the data form and that
the tank has been leak-checked (on-site).
After the new tank is attached to  the sample
train, proceed with the sampling until the
required minimum sampling time has been
exceeded.
  4.1.5   Post Test Leak Check  A  leak check
is mandatory at the conclusion  of each  test
run. After sampling is completed,  remove the
probe from the stack and plug the probe tip
Open the sample train flow shut-off valve
and monitor the sample tank vacuum gauge
for a period of 10 minutes. The leak check is
acceptable  if no visible change  in the tank
vacuum gauge occurs. Record the post test
leak rate (cm Hg per 10 minutes).  If the
sampling train does not pass the post leak
check, invalidate the run or use a procedure
acceptable  to the Administrator to adjust the
data.
  4.2  Sample Recovery. After  the post test
leak check is completed, disconnect the
condensate trap at the flow metering system
and tightly  seal both ends of the condensate
trap. Keep the trap packed in dry ice until the
samples are returned to the laboratory far
analysis. Remove the flow metering system
from the sample tank. Attach the  U-tube
manometer to the tank (keep length of
connecting line  to a minimum) and record the
final tank vacuum (P,); record the tank
temperature (TJ and barometric pressure at
this time. Disconnect the manometer from the
tank. Assure that the test run number is
properly identified on the condensate trap
and the sample tank(s).
  4.3  Condensate Recovery and
Conditioning. Prepare the condensate
recovery and conditioning apparatus by
setting the carrier gas flow rate and heating
the catalyst to its operating temperature.
Prior to initial use of the condensate recovery
and conditioning apparatus,  a system
performance test must be conducted
according to the procedures established in
section 5.1  of this method. After successful
completion of the initial performance test, the
system is routinely used for sample
conditioning according to the following
procedures:
   4.3.1  System Blank and Catalyst
Efficiency Check. Prior to and immediately
following the conditioning of each set of
sample traps, or on a daily basis (whichever
occurs first) conduct the carrier gas blank test
and catalyst efficiency test as specified in
sections 5.1.1 .and 5.1.2 of this method. Record
the carrier gas initial and final blank values.
BU and B«, respectively. If the criteria of the
tests cannot be met, make the necessary
repairs to the system before proceeding.
   4.3.2  Condensate Trap Carbon Dioxide
Purge and  Sample Tank Pressurizstion. The
first step in analysis is to purge the
eondenaate trap of any CCs which il may
contain and to simultaneously pressurize the
sample tank. This is accomplished as follows:
Obtain both the sample tank and condensate
trap from the test run  to be analyzed- Set up
the condensate recover} and conditioning
apparatus so that the carrier flow bypass**
the condensate trap hook-up terminals.
bypasses the oxidation catalyst, and is
vented to the atmosphere. Next, attach the
condensate trap to the apparatus and pack
the trap in dry ice. Assure that the valves
isolating the collection vessel connection
from the atmospheric  vent and the vacuum
pump are closed and then attach the sample
tank to the system as  if it were the
intermediate collection vessel. Record the
lank vacuum on the laboratory data furrr.
Assure that the NDIR analyzer indicates a
zero output level and  then switch the carrier
flow through the condensate trap.
immediately switch the carrier flow from vent
to collect. The condensate trap recovery and
conditioning apparatus should now be se> up
as indicated in Figure 8  Monitor the S'DIF
when COi is no longer being passed ihr" uh
the system, switch the carrier flow  so thai TI
once again bypasses the condensale trap
Continue in this manner until the gas sample
tank is pressurized to a nominal gau?e
pressure of 800 mm Hg. At this time isolate
the tank, vent the carrier flow, and  record the
sample tank pressure (P«). barometric
pressure (PM). and ambient temperature (Td).
Remove the sample tank from the system
   4.3.3  Recovery of  Condensate Trap
Sample. Oxidation and collection of the
sample in the condensate trap is now ready
to begin. From the step just completed :r.
section 4.3.1.2 above, the system should b<-
set up so that the carrier flow bypasses \ftt-
condensate trap, bypasses the oxidation
catalyst, and is vented to the atmosphere
Attach an evacuated intermediate  col't- '.;•-,
vessel to the system and then switch trip
carrier so that it flows through the  oxidation
catalyst. Switch the carrier from vent to
collect and open the valve to the coMpct'cn.
vessel; remove the dry ice from the trap anrl
then switch  the carrier flow through the trap
The system should now be set up to ope:,i>
as indicated in Figure 9. During oxidation of
the condensate trap sample, monitor the
NDIR to determine when all the sample VMS
been removed and oxidized (indicated by
return to baseline of NDIR analyzer outpui)
Begin heating the condensate trap  and probe
 with a propane torch. The trap should be
 heated to a temperature at which the trap
glows a "dull red" (approximately  500'C)
 During the early part of the trap "bun! out,"
 adjust the carrier and auxiliary oxygen flow
 rates so that an excess of oxygen is being fed
 to the catalyst system. Gradually increase the
 flow of carrier gas through the trap. After the
 NDIR indicates that most of the organic
 matter has been purged, place the  trap in a
 muffle fumance (500'C). Continue  to heat the
 probe with a torch or some other procedure
 (e.g., electrical resistance heater).  Continue
 this procedure for at least 5 minutes after the
 NDIR has returned to baseline. Remove the
 heal from the trap but continue the carrier
 flow until the intermediate collection vessel
 is pressurized to a gauge pressure  of 800 mm
                                                          25-39

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              Federal  Register /  Vol. 45.  No.  194  / Friday. October 3. 1980 /  Rules and-Regulations
Hg (noT.;r.al). When the vessel is pressurized.
vent the carrier measure and record the final
intermediate collection vessel pressure (P,j as
well as the barometric pressure (?„.), ambient
temperature (T.). and collection vessel
volume (Vv).
  4 4 Analysis. Prior to putting the NMO
anahzer i.-.to routine operation, an initial
performance test must be conducted. Start
the analyzer and perform all the necessary
functions in crder to put the analyzer in
proper working order, then conduct the
performance test according to the procedures
estabi shed in section 5.2. Once the
performance test has been successfully
completed and the Cd and NMO calibration
response factors determined, proceed with
sample analysis a* follows:
  4.4.1  Daily operations and calibration
checks. Prior to and immediately following
trie analysis of each set of samples or on a
daily basts (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
she N'MO analyzer performance test (section
52| before proceeding.
  4.4.2  Analysis of Recovered Condensate
Sample. Purge the sample loop with sample
find then inject a preliminary sample in order
to determine the appropriate FID attenuation.
Inject triplicate samples from the
intermediate collection vessel and record the
values obtained for the condensible organic*
   4.4.3  Analysis of Sample Tank. Purge the
 sumple loop with •ample and inject a
 preliminary sample in order to determine the
 appropriate FID attenuation for monitoring
 the backfhished non-methane organics. Inject
 triplicate samples from the sample tank and
 record the values obtained for the
 nonmethane organics (Q_).

 5. Calibration and Operational Checks
   Maintain a record of performance of each
 item.
   5.1 Initial  Performance Check of
 Condensate Recovery and Conditioning
 Apparatus.
   5.1.1  Carrier Gas and Auxiliary Oxygen
 Blank. Set equal flow rate* for bom the
 carrier gas and auxiliary oxygen. With the
 trap switching valve* in the bypass position
 and the catalyst in-line, fill an evacuated
 intermediate collection vessel with carrier
 gas. Analyze the collection vessel for CO*
 the carrier blank i» acceptable if the CO,
 concentration is less than 10 ppm.
  8.1.2  Catalyst Efficiency Check. Set up the
 Condensate trap recovery system so that the
 carrier flow bypasses the trap inlet and is
 vented to the  atmosphere at the system
 outlet Assure that the valve* isolating the
 collection system from the atmospheric vent
 and vacuum pump are dosed and men attach
 an evacuated  intermediate collection vessel
 to the system. Connect the methane standard
ga* cydinder  (section 34.1) to the system's
condensate trap connector (probe end. Figure
 4). Adjust the  system valving so that the
 standard ga* cylinder act* a* the carrier ga*
 and adjust the flow rate to the rate normally
 used during trap sample recovery. Switch off
 the auxiliary oxygen flow and men switch
 from vent to collect in order to begin
collecting a sample. Continue collecting a
 sample in a normal manner until the
 intermediate vessel is filled to a nominal
 gauge pressure of 300 mm Hg. Remove the,
 intermediate vessel from the system and vent
 the carrier flow to the atmosphere. Switch the
 valving to return the sy*tem to it* normal
 carrier gas and normal operating conditions.
 Analyze the collection vessel for CCs; the
 catalyst efficiency is acceptable if the CO,
 concentration is within ±5 percent of the
 expected value.
  5.1.3  System Performance Check.
 Construct a liquid sample injection unit
 similar in design to  the unit shown in Figure
 6. Insert this unit into the condensate
 recovery and conditioning system in place of
 a condensate trap and set the carrier ga* and
 auxiliary oxygen flow rates to normal
 operating levels. Attach an evacuated
 intermediate collection vessel 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 (sea.  5.1.3.1  to 5.1.3.4) via the injection
 septum. Heat the injection unit with a torch
 while monitoring die oxidation reaction on
 the NDIR. Continue the purge until the
 reaction is complete. Measure the final
 collection vessel pressure and then analyze
 the Vessel to determine the CO,
 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
 6.7) of less than S percent for each set of
 triplicate injection* a* follows:
  5.1.3.1  lOOulhwcane.
  M44  lOpJhexane.
  5.1.3 J  100 fd toluene,
  5.1.3.4  10 jj toluene.
  5.2   Initial NMO  Analyzer Performance
 Te*t
  5.2.1  Oxidation Catalyst Efficiency Check.
 Turn off orbypaw the NMO analyzer
 reduction catalyst Make triplicate injection*
of the high level methane standard (section
3.3.1). The oxidation catalyst operation is
acceptable if no FID n*pon*a i* noted.
  5.t2  Analyzer Linearity Check and NMO
Calibration. Operating both the oxidation and
reduction catalyst*,  conduct a linearity check
of the analyzer using the propane standards
specified in section 34. make triplicate
injection* of each calibration ga* and then
calculate the  average response factor (area/
ppm C) for each gas, a* well a* the overall
mean of the re*pon*e factor value*. The
instrument linearity hi acceptable if the
average response factor of each calibration
gasis within  ±5 percent of the overall mean
value and if the relative standard deviation
(section S-7) for each set of triplicate
injection* i* lea* than ±5 percent Record the
overall mean of the  propane re*pon*e factor
 value* as the NMO calibration respon*e
  5.2.3  Reduction Catalyst Efficiency Check
and CO, Calibration. An exact determination
of the reduction catalyst efficiency I* not
required. Instead, proper catalyst operation i*
indirectly checked and
monitored by establishing a CO, response
factor and comparing it to the NMO response
factor. Operating both die oxidation and
reduction catalyst* make triplicate injection*
of each of the CO, calibration ga*e* (section
3.3.3). Calculate the average response factor
 (area/ppm) for each calibration gas, as well
 as the overall mean of the response factor
 values. The reduction catalyst operation is
 acceptable if the average response factor of
 each calibration ga* is within ±5 percent of
 the overall mean value and if the relative
 standard deviation (section 6.7) for each set
 of triplicate injection* i* les* than ± 5
 percent. Additionally, the CO, overall mean
 response factor must be within ± 10 percent
 of the NMO calibration response factor
 (&Pmn) calculated in section 522. Record the
 overall mean of the response factor values as
 tha CO, calibration response factor (RFc<»)<
   5.2.4  NMO System Blank. For the high
 level CO, calibration gas (section 344)
 record the NMO value measured during the
 CO, calibration conducted in section 5.2.3.
 This value i* the NMO blank value for the
 analyzer (BJ and should be leu' than 10 ppm.
   5A3  System Performance Check. Check
 the column separation and overall
 performance of the analyzer by making
 triplicate injection* of the calibration gases
 listed in section 3.3.4. The analyzer
 performance i* acceptable if the measured
 NMO value for each ga* (average of triplicate
 injection*) i* within ± 12 percent of the
 expected value.
   5.3  NMO Analyzer Daily Calibration.
   5.3.1  NMO Blank and CO» Inject
 triplicate samples of the high level CO,
 calibration ga* (section 344) and calculate
 the average response factor. The system
 operation la adequate if the calculated
 response factor i* within  ± 10 percent of the
 RFcot calculated during the initial
 performance test (section 5i2). Use the daily
 response factor (DRF,*) for analyzer
 calibration and the calculation of measured
 CO, concentrations in the collection vessel
 (ample*. In addition, record the NMO blank
 value (BJ: this value should be less than 10
 ppm.
  5.3.2  NMO Calibration. Inject triplicate
 samples of the mixed propane calibration
 cylinder (section 34.4.1) and calculate the
 average NMO response factor. The system
 operation is adequate if the calculated
 response factor is within ± 10 percent of the
 RFxMo calculated during the initial
 performance test (section 54.1). U*e lite daily
 response factor (DRFuMo)  for analyzer
 calibration and calculation of NMO
 concentrations in the sample tanks.
  5.4   Sample Tank. The-volume of the gas
 sampling tanks used must be determined.
 Prior to putting each tank in service,
 determine the tank volume by weighing the
 tanks empty and then filled with deionired
 distilled water; weigh to the nearest 5 gm and
 record the result*. Alternatively, measure that
 volume of water used to fill the tank* to the
 nearest 5 mL
  5.5   Intermediate Collection Vessel The
 volume of the Intermediate collection vessel*
used to collect CO, during the analysi* of the
condensate trap* must be determined. Prior
to putting each vessel into service, determine
the volume by weighing the vessel empty and
 then filled with deionixed distilled water;
weigh to the nearest 5 gm and record the
results. Alternatively, measure the volume of
water used to fill the tanks to the nearest 5
ml.
                                                           25-40

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ro
en
 i
      6.  Calculations
           Note:  All equations are written using absolute pressure;
      absolute pressures are determined by adding the measured barometric
      pressure to the measured gauge pressure.
           6.1  Sample Volume.  For each test run, calculate the gas
      volume sampled;
                     0.386 V
                                t    t1
            6.2  Noncondenslble Organlcs.  For each sample tank, determine
       the concentration of  nonmethane organlcs  (ppm C):
                 ct"
                           tf

                              ti
£   r   C^  - B,
r  JBl   tin.,    a
            6.3  Condenslble Organlcs.   for each  condensate  trap determine
       the concentration of organlcs (ppm C):
                      0.386
                             vp
     6.4  Total Gaseous Nonmethane Organlcs (TGNMO).  To determine
the TGNMO concentration for each test run. use the following
equation:
     6.S  Total Gaseous Nonmethane Organlcs (TGNHO) Mass
Concentration.  To determine the TGNHO mass concentration as
carbon for each test run, use the following equation:
                                                                                        Mr • 0.498 C
     6.6  Percent Recovery.   To calculate the percent recovery for
the liquid Injections to the compensate recovery and conditioning
system use the following equation:
                                                                                                               o
                                                                      in
                                                                      z
                                                                      o
a
cu
><
o
n
                                                                              V   P   C
                                                                           M   v   f   I
                                                    percent recovery •  1.6  r;  p   "T" ~1
                                                                                   6.7  Relative Standard Deviation.
                                              cm
                                                                                        RSO
                                                                                                          n -
                                                                     »
                                                                     c^
                                                                     5*
                                                                     <•
                                                                     »
                                                                     a.
                                                                                                                                                    o

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             Federal Register / Vol. 45. No.  194  /  Friday. October 3. 1980  /  Rules and  Regulations
Where:
B. = Measured NMO blank value for NMO
    analyzer, ppm C.
B. = Measured CO, "-* «•"" '" «"*"— «•—• »
    .« coMiimuw mum anur w. n» COf
C = total gaseous nonmethane organic
    (TCNMO) concentration of the effluent
    ppm C equivalent
C,= Calculated condensible organic
    Icondensate trap) concentration of the
    effluent, ppm C equivalent
Cj,, = Measured concentration (NMO
    anjlyzerj for the condensate trap
    (intermediate collection vessel), ppm
    CO,
C,- Calculated noncondensible organic
    concentration (sample tank) of the
    effluent, ppm C equivalent
C,n= Measured concentration (NMO
    analyzer) for the sample tank, ppm NMO.
L = Volume of liquid injected, microliten.
M = Molecular weight of the liquid injected.
    g/gmole.
Mc - total gaseous non-methane organic
    ( J'CN'MO) mass concentration of the
    eftluem. mji C/dscm.
N = Carbon number of the liquid compound
     injected (N = 7 for toluene. N » ft for
     hpxane).
 P, = Final pressure of the intermediate
     collection vessel, mm Hg absolute.
 Pu -GuS sample tank pressure prior  to
     sampling, mm Hg absolute.
 P, =CdS sample tank pressure after sampling.
     b'i; prior to pressurizing, mm tig
     absolute.
  Pj = Final «as sample Unk pressure after
     pressurizing. .Tim Mg nhsaiute.
  T,=Fir,dl temperature of intermediate
     collection vessel. 'K.
  T,, = Sample tank temperature prior to
     sampling. 'K.
  T, -Sample tank temperature at completion
     of sampling. K.
  Tus=S.tmple tank temperature after
     pressurizing 'K.
  V = Sample lank volume, cm.
  V,ssi:iterr.ediate collection vessel volume.
     cm
  V, -das volume sampled, dstm
 n =Number of Juta points.
  q » Total number of analyzer injections of
     intermediate collection vessel during
     iir.:il)sis (where k = injection number. 1
         qi
  r -Total number of analyzer ir.|fctions of
     Viffipie tank during analjsis (where
     i - init;r.i;un number. 1 . . . r|.
  x, = l;.Jindudl measurements.
  X=Mcun value.
  p=Onsity of liquid injected. g/r.c.
   7.1   S.id.. Ai! TI E . Samuol W'.tz. and
  Rul*n 0 MJI I'lice Duterminjtion of Solvent
  Vjpor CotiLfRiracons by Total Combustion
  Analysis \ Cjinj-uiison of Infrared with
  F'.jme loiiization Detectors. Paper No. 75-33.2
  (Presenti-d at '.ht- ftifh Annual Meeting of the
  Air Pollution Control Association. Boston.
  MA. lune 15-20. 1975 1 14 p.
   7 z  S^lo. Albert £.. William L Oaks, and
  Robtrt 0. MacPhee. Measuring the Organic
  Carbon Content of Source Emissions for Air
  Pollution Control. Paper No. 74-190.
  (Presented dt the 67th Annual Meeting of the
  Air P')i'. it:on Control Association Denver.
  CO  June *-\3. 1974 ) 23 p.
Method 25

Addendum I. System Components
  In test Method 25 several important system
components are not specified; instead
minimum performance specifications are
provided. The method if written in this
manner to permit individual preference in
choosing component*, u well as to
encourage development and use of improved
components. This addendum is added to the
method in order to provide users with some
specific information regarding components
which have been found satisfactory for use
with the method. This listing is given only for
the purpose of providing information and
does not constitute an endorsement of any
product by the Environmental Protection
Agency. This list is not meant to imply that
other components not listed are not
acceptable.
  1. Condensate Recovery and Conditioning
System Oxidation  Catalyst. H" OD x 14"
inconel tubing pecked with 8 inches of
hopcalite* oxidizing catalyst and operated at
atxrC in a tube furnace. Note: At this
temperature, this catalyst must be purged
with carrier gas at all times to prevent
catalyst damage.
   Z. NMO Analyzer Oxidation Catalyst *•'
 OD A 14" inconel tubing packed with 8 inches
 of hopcalite oxidizing catalyst and operated
 at 800'C in a tube  furnace. (See note above.).
   3. NMO Analyzer Reduction Catalyst.
 Reduction Catalyst Module: Byron
 Instruments. Raleigh. N.C.
   4. Gas Chromatographic Separation
 Column. Vfe inch OD stainless steel packed
 with 3 feet of 10 percent methyl silicone. Sp
2100 (or equivalent) on Supelcoport (or
 equivalent). 80/100 mesh, followed by 1.3 feet
Porapak Q (or equivalent) 80/80 mesh. The
inlet side is to the  silicone. Condition the
column for 24 hours at 200'C with 20 cc/min
N, purge.
   During analysis  for the nonmethane
organics the separation column is operated as
follows: First operate the column at -78*C
(dry ice bath) to eiute CO and CH* After the
CH, peak operate  the column at O'C to elute
CO*. When the CO, is completely eluted.
 switch the carrier  flow to backfluah the
 column and simultaneously raise the column
 tempera hire to 100'C in order to elute all
 nonmethane organic* (exact timings for
 column operation  are determined from the
 calibration standard).
   Note.—The dry  ice operating condition
 may be deleted if separation of CO and CH.
 is unimportant
   Note.—Ethane and ethylene may or may
 not be measured using thjs column: whether
 or not ethane and ethylene are quantified will
 depend on the CO> concentration in the gas
 sample. When high levels of CO, are present.
 ethane and ethylene will elule under the tail
 of the CO, peak.
   S. Carrier Cas. Zero grade nitrogen or
 helium or zero air.
   •MSA rrgulered
                                                           25-42

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Federal Register / Vol. 45. No. 194 / Friday, October 3,1980 / Rules and Regulations
'

PROBE
EXTENSION
(IF REQUIRED)

B.-.
SI
w
r




••
A
At
Jl
t





PROBE \
\ *
•K \
•l \
1 V]
L
1 	 '
1
DRY ICE
AREA
Tj
1
VACUUM
GAUGE
FLOW S\\
^^ RATE \\J
] CONTROLLER J
1 ^a*.
iStT- &i
1 Ix^sJ VV
L ON/OFF
-J,_ FLOW
|J*\ VAIVI QUICK f±l
CONNECTOR CONNECT^
^ /^\
f 1



mmmm
1 	
CONDENSATE EVACUATED
TRAP SAMPLE
TANK
                  Figure 1. Sampling apparatus
                                  25-43

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           Federal Register /  Vol. 45. No. 194 / Friday. October 3. 1980 / Rules and Regulations
                             CARRIER GAS
CALIBRATION STANDARDS.


         SAMPLE TANK-
        INTERMEDIATE
         COLLECTION
           VESSEL
   (CONDITIONED TRAP SAMPLE)
   1
 SAMPLE
INJECTION
  LOOP
                                          1ACKFLUSH
                                            NON-METHANE
                                             OR6ANICS
                                                      •HYDROGEN
                                FLAME
                              IONIZATION
                              DETECTOR
                       .COMBUSTION
                           AIR
                                 DATA
                              RECORDER
Figure 2.  Simplified schematic of non-methane organic  (NMO)  analyzer.
                                          25-44

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                                                                                                    SAMPLE /CALIBRATION
                                                                                                    TANK  / CYLINDERS
ro
in
-p=«
en
                                                            SEPARATION
                                                              COLUMN
                                                  NONMETHANE
                                                    ORGANIC
                                                  (BACKFLUSH)
                                                                                                QUICK
                                                                                               CONNECT
CATALYST
 BYPASS
                             CULUMN
                            BACKFLU
                             VALVE
                              CATALYST
                             BYPASS VALVE
                                                 INJECT
                                                 VALVE
                              OXIDATION
                              CATALYST
    HEATED
    CHAMBER     j
    GAS
PURIFICATION
  FURNACE
MOLECULAR
  SIEVE
   CATALYST
    BYPASS
              FLOW
            REGULATOR
                                 ATALYS
                                 BYPASS
                                 VALVE
                              REDUCTION
                               CATALYST
                         I   HEATED CHAMBER
                                                                                       DATA
                                                                                     RECORDER
                                                     2
                                                     CL
                                                                                                         I
                                                                                                                           FLOW
                                                                                                                          METER
                                                                                                                                    E.
                                                                                                                                    S
                                                                                                         D
                                                                                                         O.
                                                                                                         «w
                                                                                                         i
                                           Figure 3. Nonmethane organic (NMO) analyzer.

-------
           Federal Regbtor / Vol. 45. No. 194 / Friday. October 3.1980 / Rules and Regulations
                      FLOW
                      METERS
                      FLOW
                     CONTROL
                     VALVES \
                                      SWITCHING
                                      VALVES
                                            SAMPLE
                                           CONOENSATE
                                             TRAP
CARRIER
<5ptrc«tit
 02/N2
                                                                               OXIDATION
                                                                               CATALVST
                                                                                 HEATED     I
                                                                                CHAMBER
                                                 VENT  HEAT
                                                              NOIR
                                                            ANALYZER
                           REGULATING
                            VALVf
                                     FOR MONITORING PROGRESS
                                       OF COMBUSTION ONLY
                              QUICK r
                             CONNECTjgl
VALVE
   VACUUM**
    PUMP
 MERCURY
MANOMETER
                    -FOR EVACUATING COLLECTION
                     VESSELS AND SAMPLE TANKS
                             (OPTIONAL)
                      Figure 4.  Condensate recovery and conditioning apparatus.
                                          25-46

-------
                                            194  /  Friday. October 3. 1960  /  Rules and Regulations
                                                      PROBE, 3mm (I/In) 0.0.

                            INLET TUB£. 6mm ('A in) O.D.          V
          CONNECTOR
EXIT TUBE. 6mm (14 in) 00
   NO. 40 HOLE
(THRU BOTH WALLS)
      WELDED JOINTS
                                        CRIMPED AND WELDED GAS TIGHT SEAL
                                    VBARREL 19mm (4 in) 0.0. X 140mm (5 % mi LONG
                                               1.5mm (1/16 in) WALL
                                      BARREL PACKING.  316 SS WOOL PACKED TIGHTLY
                                              AT BOTTOM. LOOSELY AT TOP
                                      HEAT SINN {NUT. PRESS-FIT TO BARREL)
                                     WEIOEO PLUG
              MATERIAL  TYPE 316 STAINLESS STEEL

                         Figure 5  Condensau;
                                                 25-47

-------
            Federal Register / Vol. 45. No. 194 / Friday. October 3.1980 /  Rules and Regulations
                                INJECTION
                                SEPTUM
        CONNECTING T
FROM
CARRIER
               AffROX.
              IS cm IS m)
                   I
                                               CONNECTING
                                               ELBOW
                                                                 TO
                                                                 CATALYST
                                                      6 mm (1/4 m)
                                                      311 SS TUBING
                 Figure 6.  Liquid sample  injection unit
                                            25-48

-------
           Federal Register / Vol. 45. No. 194  /  Friday, October 3. 1980 / Rules and Regulations
                                   VOLATILE ORGANIC CARBON
FACILITY—
LOCATION.
DATE	
             SAMPLE LOCATION.
             OPERATOR	
              RUN NUMBER.
TANK NUMBER.
 _TRAPNUMBER.
                                                              .SAMPLE 10 NUMBER.
TANK VACUUM.
mm H| cm Hj
PRETEST (MANOMfTFR)
POST TEST (MANOMETER!


(GAiir.fi

BAROMETHIC
PRESSURE.
mm Hg


AMBIENT
TEMPERATURE.
°C


LEAN RATE
on H| / 10 tnin

TIME
CLOCK/SAMPLE


















WIST TKT
GAUGE VACUUM.
em HI



















FLOWMETER SETTING














-




COMMENTS '


!















                                 Figure 7.  Example Field Data Form
                                              25-49

-------
Federal Register / Vol. 45. No. 194 / Friday. October 3.1980 /  Rules and Regulations
-
(
\ FLOW TR4P f
/" METERS ^ ™"
r~) i — MX d1
Tn T ^ ftow T"1"
it U CONTROL ,
,11 ,11, ^ VALV" >ffU i
i r i-iSl^i 	 rs^ r
i — 1 I — r v*vl , ls*^J L—
(OPEN) {OPEN)
SWITCHING
S1 VALVES H-, , ,
f 1 \ I'XJ— —m
CONNECVORS

' 	 ("PURIFIER r
T
L- txKl 	 [ PURIFIER J
(CLOSED)
A f
CAR
02 *5P*
02
.1
1 r-
RIER |
rcentj |
<*l 1
1
I
' 7 n
X 'ROBE I
/ K>
v ^
-4— — — I
| SAMMP 1 H— -
CATALYST
BYPASS
VENT 1
trV
»WAY ^-/
ALVES-^I
	 (-,
I CONDENSATE; | OXIDATION |
{ TRAP 1 | CATALYST J

» Hr- «nr.« j . Cl
VENT
A
•~&* "KarX
T"^ (OPEN) T^
OUICK Ai
1 CONNECTJQf
(CLOSEOlV-J) [**
•J * «
V
Tu"^ MERCURY "SSSSS?
MANOMETER COLLECTION
VESSEL


NOIR ^
ANALYZER*

EATEO |
(AMBER i

1 |
1 1
)R MONITORING PROGRESS
OF COMBUSTION ONLY
H20
TRAP
••FOR EVACUATING COLLECTION
VESSELS AND SAMPLE TANKS
(OPTIONAL)
   Figure 8,  Condensate recovery  and conditioning apparatus, carbon dioxide purge.
                                    Z5-50

-------
            Federal Register  /  Vol. 45, No. 194 / Friday, October 3.1980 / Rules and Regulations
                                                                 SAMPLE
                                                               CONOENSATE
                                                                  TRAP
                                                                                       VINT

                                                                                         tf>,
                                                                                     4WAV  X_^X
                                                    VENT   HEAT
                (OPENI
ICLOSEOI
          REGULATING
             VALVE
             (OPEN)
             QUICK
            CONNECT
    VACUUM-
      PUMP
                                                                 NOIR
                                                               ANALYZER'
                       FOR MONITORING PROGRESS
                         OF COMBUSTION ONLY
                                                                                      \/
                                                                                       H20
                                                                                       TRAP
 MERCURY
MANOMETER
INTERMEDIATE
 COLLECTION
   VESSEL
•FOR EVACUATING COLLECTION
 VESSELS ANO SAMPLE TANKS
         (OPTIONAL)
            Figure 9.  Corxlensatc recovery and condiT.on.ng apparatus, collection of trap organic*
                                           25-51

-------
40 CFR Part 60, Appendix A
Final, promulgated
                  METHOD  25A - DETERMINATION  OF TOTAL  GASEOUS  ORGANIC
                    CONCENTRATION  USING A  FLAME IONIZATION  ANALYZER
         1.    Applicability  and Principle
              1.1  Applicability.   This method applies  to the measurement  of
         total  gaseous  organic concentration  of vapors  consisting  primarily of
         alkanes,  alkenes,  and/or  arenes  (aromatic hydrocarbons).   The  concentration
         is  expressed  in  terms of  propane  (or other appropriate organic calibration
         gas)  or in  terms of carbon.
              1.2   Principle.  A  gas  sample is extracted from the source
         through a heated sample  line, if  necessary, and glass fiber filter to
         a flame ionization analyzer  (FIA).  Results are reported as volume
         concentration equivalents of the  calibration gas or as carbon equivalents.
         2.   Definitions
              2.1   Measurement System.  The total  equipment  required for the
         determination of the gas concentration.  The system consists of the
         following major subsystems:
              2.1.1   Sample Interface.  That  portion of  the  system that is used
         for one or more of the following:  sample  acquisition, sample
         transportation, sample conditioning,  or  protection  of the analyzer
         from the effects of the stack effluent.
              2.1.2  Organic Analyzer.  That  portion of  the system that senses
         organic  concentration and generates  an output proportional  to the gas
         concentration.
               2.2   Span  Value.   The  upper  limit of a  gas concentration
         measurement  range  that  is specified for  affected source categories  in
                                         25A-1

-------
the .applicable part of the regulations.  The  span  value  is  established
in the applicable regulation and is usually 1.5  to 2.5 times  the
applicable emission limit.  If no span value  is  provided, use a span
value equivalent to 1.5 to 2.5 times the expected  concentration.   For
convenience, the span value should correspond  to 100 percent  of the
recorder scale.
     2.3  Calibration Gas.  A known concentration  of a gas  in an
appropriate diluent gas.
     2.4  Zero Drift.  The difference  in the  measurement system response
to a zero level  calibration gas before and after a stated period  of
operation during which no unscheduled maintenance, repair,  or adjustment
took place.
     2.5  Calibration Drift.  The difference  in  the measurement system
response to a mid-level calibration gas before and after a  stated
period of operation during which no unscheduled  maintenance,  repair,
or adjustment took place.
     2.6  Response Time.   The time interval from a step change in
pollutant concentration at the inlet to the emission measurement
system to the time at which 95 percent of the  corresponding final
value is reached as displayed on the recorder.
     2.7  Calibration Error.  The difference  between the gas  concentration
indicated by the measurement system and the known  concentration of the
calibration gas.
3.   Apparatus
     A  schematic of  an acceptable measurement  system is  shown in
Figure  25A-1.  The essential components of the measurement  system are
described  below:
                                  25A-2

-------
                    I'HOUE
                                                            HEATED
                                                            SAMPLE
                                                            LINE
ro
ui
                PARTICULATE
CALIBRATION       FILTER
   VALVE
                                                                                           ORGANIC
                                                                                          ANALYZER
                                                                                             AND
                                                                                          RECORDER
                                                                     SAMPLE
                                                                      PUMP
                   STACK
                                Figure 2BA-1.  Oifjunic Concentration Measnrenicni System.

-------
     3,1  Organic Concentration Analyzer.  A flame  ionization  analyzer
(F!A) capable of meeting or exceeding the specifications  in  this
method.
     3.2  Sample Probe.  Stainless steel, or equivalent,  three-hole
rake type.  Sample holes shall be 4 mm  in diameter  or smaller  and
located at 16.7, 50, and 83.3 percent of the equivalent stack  diameter.
Alternatively, a single opening probe may be used so that a  gas sample
is collected from the centrally located 10 percent  area of the stack
cross-section.
     3.3  Sample Line.  Stainless steel or Teflon*  tubing to transport
the sample gas to the analyzers.  The sample line should  be  heated,  if
necessary, to prevent condensation in the line.
     3.4  Calibration Valve Assembly.   A three-way  valve  assembly  to
direct the zero and calibration gases to the analyzers  is recommended.
Other methods, such as quickrconnect lines, to route calibration gas
to the analyzers are applicable.
     3.5  Parttculate Filter.  An in-stack or an out-of-stack  glass
fiber filter is recommended if exhaust  gas particulate  loading is
significant.  An out-of-stack filter should be heated to  prevent any
condensation.
     3.6  Recorder.  A strip-chart recorder, analog computer,  or
digital recorder for recording measurement data.  The minimum  data
recording.requirement is one measurement value per  minute.   Note:  This
method  is often applied in highly explosive areas.  C'aution  and care
should  be exercised in choice of equipment and installation.
""Mention of trade names or specific products does not constitute
endorsement by the Environmental Protection Agency.
                                  75A-4

-------
 4.   Calibration  and  Other  Gases
     Gases used  for  calibrations,  fuel,  and combustion air (if required)
 are  contained  in compressed  gas  cylinders.   Preparation of calibration
 gases shall be done  according  to  the  procedure in Protocol  No. 1,
 listed  in Reference  9.2.   Additionally,  the manufacturer of the cylinder
 should  provide a recommended shelf life  for each calibration gas
 cylinder over which  the concentration does  not change more than ±2
 percent from the certified value.   For calibration gas values not
 generally available  (i.e., organics between 1 and 10 percent by
 volume), alternative methods for  preparing  calibration gas mixtures,
 such as dilution systems, may  be  used with  prior approval  of the
 Administrator.
     Calibration gases usually consist of propane in air or nitrogen
 and are determined in terms of the span  value.   Organic compounds  other
 than propane can be used following the above guidelines and making the
 appropriate corrections for response  factor.
     4.1  Fuel.  A 40 percent H2/60 percent He or 40 percent H2/60
 percent N2 gas mixture is recommended  to avoid- an oxygen  synergism
 effect that reportedly occurs when^oxygen concentration varies
 significantly fron a mean value.
     4.2  Zero Gas.  High purity  air  with less than  0.1  parts  per
million by volume (pptnv) of organic material  (propane  or  carbon  equivalent)
 or less than.0.1 percent of the span  value,  whichever  is  greater.
     4.3  Low-level Calibration Gas.   An organic calibration gas with
 a concentration equivalent to 25  to 35 percent of the  applicable span
 value..
                                  25A-5

-------
     4.4  Mid-level  Calibration Gas.  An organic calibration gas with
a concentration equivalent to 45 to 55 percent of the applicable span
value.
     4.5  High-level  Calibration Gas.  An organic calibration gas with
a concentration equivalent to 80 to 90 percent of the applicable span
value.
5.  Measurement System Performance Specifications
     5.1  Zero Drift.   Less than ± 3 percent of the span value.
     5.2  Calibration Drift.  Less than ± 3 percent of the span value.
     5.3  Calibration Error.  Less than ± 5 percent of the calibration
gas value.
6.  Pretest Preparations
     6.1  Selection of Sampling Site.  The location of the sampling
site is generally specified by the applicable regulation or purpose  of
the test; i.e., exhaust stack, inlet line, etc.  The sample port.shall
be located at least 1.5 meters or 2 equivalent diameters (whichever  is
less) upstream of the gas discharge to the atmosphere.
     6.2  Location of Sample Probe.  Install the sample probe so that
the probe is centrally located in the stack, pipe, or duct and is
sealed tightly at the stack port connection.
     6.3  Measurement System Preparation.  Prior to the emission test,
assemble the measurement system following the manufacturer's written
instructions in preparing the sample interface and the organic analyzer,
Make the system operable.
     FIA equipment can be calibrated for almost any range of total
organics concentrations.  For high concentrations of organics (>1.0
percent by volume as propane) modifications to most commonly available
                                   25A-6

-------
analyzers are necessary.  One accepted method of  equipment modification
is to decrease the size of the sample to the analyzer  through  the use
of a smaller diameter sample capillary.  Direct and  continuous measurement
of organic concentration is a necessary consideration  when determining
any modification design.
     6.4  Calibration Error Test.  Immediately prior to  the test series,
(within 2 hours of the start of the test)  introduce  zero gas and high-
level calibration gas at the calibration valve assembly.  Adjust the
analyzer output to the appropriate levels,  if necessary.  Calculate
the predicted response for the low-level and mid-level gases based on
a linear response line between the zero and high-level-responses.
Then introduce low-level and mid-level calibration gases successively
to the measurement system.  Record the analyzer responses for  low-level
and mid-level calibration gases and determine the differences  between
the measurement system responses and the predicted responses.  These
                                       *,
differences must be less than 5 percent of  the respective calibration
gas value.  If not, the measurement system  is not acceptable and must
be replaced or "repaired prior to testing.   No adjustments to the
measurement system shall be conducted after the calibration and before
•uhe drift check (Section 7.3).  If adjustments are necessary before
the completion of the test series, perform  the drift checks prior to
the required adjustments and repeat the calibration  following  the
adjustments.  If multiple electronic ranges are to be  used, each
additional range must be checked with a mid-level calibration  gas  to
verify the multiplication factor.
                                 25A-7

-------
     6.5  Response Time Test.   Introduce  zero gas into the measurement
system at the calibration valve  assembly.   When the system output has
stabilized, switch quickly to  the  high-level  calibration gas.   Record
the time from the concentration  change  to  the measurement system
response equivalent to 95 percent  of  the  step change.   Repeat the test
three times and average the results.
7.  Emission Measurement Test  Procedure
     7.1   Organic Measurement.   Begin sampling at the  start of the
test period, recording time and  any required  process information as
appropriate.  In particular, note  on  the  recording chart periods of
process interruption or cyclic operation.
     7.2  Drift Determination.   Immediately following  the completion
of the test period and hourly during  the test period,  reintroduce the
zero and  mid-level calibration gases, one  at  a time, to  the measurement
system at the calibration valve  assembly.   (Make  no  adjustments  to the
measurement system until  after both the zero  and  calibration drift
checks are made.)  Record the analyzer  response.   If the drift values
exceed the specified limits, invalidate the test  results  preceding the
check and repeat the test following corrections to the measurement
system.   Alternatively, recalibrate the test  measurement  system  as in
Section 6.4 and report the results using both  sets of calibration data
(i.e., data determined prior to the test period and  data  determined
following the test period).
3.  Organic Concentration Calculations
     Determine the average organic concentration  in  terms  of ppmv as
propane or other calibration gas.  The  average shall be  determined by
the integration of the output recording over  the  period  specified in
the applicable regulation.
                                 25A-8

-------
     If results are required in terns of  ppmv  as  carbon,  adjust measured
concentrations using Equation 25A-1.

                    Cc • K cmeas                            *• »*-l
Where:
     C     = Organic concentration  as carbon,  ppmv.
     C „_ • Organic concentration  as measured, ppmv.
      rneas
     K     * Carbon equivalent correction factor,
             K « 2 for ethane.
             K a 3 for propane.
             K * 4 for butane.
             K • Appropriate response factor for  other organic
                 calibration gases.

9.  Bibliography
     9.1   Measurement of Volatile Organic Compounds - Guideline Series.
U.S. Environmental Protection Agency.  Research Triangle  Park, N.C.
Publication No. EPA-450/2-78-041.   June 1978.. p. 46-54.
     9.2  Traceability Protocol for Establishing  True Concentrations
of Gases Used for Calibration and Audits  of Continuous Source Emission
Monitors (Protocol No. 1).   U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory.  Research Triangle
Park, N.C.  June 1978.
     9.3  Gasoline Vapor Emission Laboratory Evaluation - Part 2.  U.S.
          •
Environmental Protection Agency, Office of Air Quality Planning and
Standards.  Research Triangle Park, N.C.  EMB  Report  No.  75-GAS-6.
August 1975.
                                  25A-9

-------
                Federal Register / VoL 48. No. 161 / Thursday,  August  18, 1983 / Rules and Regulations
                             IMnga
  1. Applicability and Principle.
  1.1  Applicability. This method applies to
the measurement of total gaseous organic
concentration of vapors consisting primarily
of slkane*, alkenes. and/or arenes (aromatic
lydrocarbons). The concentration is
•xpiassiir] in term* of propane (or other
•p^opriate organic calibration gas) or in

  12 Principle. A gas sample is extracted
fan ne source through a heated sample line,
if •Bcenory, and glass fiber filter to a flame
tm^ytum analyser (F1A). Results are
reported as volnme concentration equivalents
of fee calibration gas or as carbon
equivalents.
  2.  Definitions.
  2.1 Measurement System. The total
equipment required for the determination of
the gas concentration. The system consists of
the following major subsystems:
  2.1.1  Sample Interface. That portion of the
system that is used for one or more of the
following: sample acquisition, sample
transportation, sample conditioning, or
protection of the analyzer from the effects of
the stack effluent.
  2.12  Organic Analyzer. That portion of
the system that senses organic concentration
and generates an output proportional to the
gas concentration.
  23 Span Value. The upper limit of a gas
concentration measurement range-that is
specified for affected source categories in the
applicable part of the regulations. The span
value is established in the applicable
regulation and is usually 1.5 to 2.5 times the
applicable emission limit If no span value is
provided, use a span value equivalent to 1.5
to &5 times the expected concentration. For
convenience, the span value should
correspond to 100 percent of the recorder
scale.
  2.3  Calibration Gas. A known
concentration of a gas in an appropriate
diluent gas,
  2.4  Zen Drift. The difference in the
measurement system response to a zero level
calibration gas before and after a stated
period of operation during which no
unscheduled maintenance, repair, or
adjustment took place,
   2JS  Calibration Drift. The difference in the
 measurement system response to a mid-level
 calibration gas before and after a stated
 period of .operation during which no
 unscheduled mainhmamre. repair or
 adjustment took place.
   2.6  Response Time. The time interval
 from a step change in pollutant concentration
/at the inlet to the emission measurement
system to the time at which 95 percent of the
 corresponding final value is reached as
 displayed on die recorder.
   2.7  Calibration Error. The difference
 between the gas concentration indicated by
 the measurement system and the  known
 concentration of the calibration gas.
   3. Apparatus.
   A schematic of an acceptable measurement
 system is shown in Figure 25A-1. The
 essential components of the measurement
 system are described below:
  3.1  Organic Concentration Analyzer. A
flame ionization analyzer (FIA) capable of
meeting or exceeding the specifications in
this method.
  33  Sample Probe. Stainless steel, or
equivalent three-hole rake type. Sample
holes shall be 4 mm in diameter or smaller
and located at M.7,50, and 8£3 percent of the
equivalent stack diameter. Alternatively, a
single opening probe may be used so that a
gas sample is collected from the centrally
located 10 percent area of the stack cross-
section.
  3.3 Sample Line. Stainless steel or Teflon*
tubing to transport the sample gas to the
analyzers. The sample line should be heated,
if necessary, to prevent condensation in  the
line.
  3.4 Calibration Valve Assembly. A three-
way valve assembly to direct the zero and
calibration gases to the analyzers is
recommended Other methods, such as quick.
•connect lines, to rente calibration gas to  the
analyzers are applicable.
  3.5 Particulate Filter. An in-stack or an
out-of-stack glass fiber-filter is recommended
if exhaust gaa particulate loading is
significanUAn out-of-stack filter should be
heated to prevent any condensation.
  &0 Recorder. A strip-chart recorder,
analog computer, or digital recorder for
PBCQfulllfl OI8ttMff8fihB&t Qtttfl* Iu9 DUmmiXDft
data recording requirement ia one
measurement value per ™™*»- Note: This •
method is often applied in highly explosive
areas. Cation and can should be exercised
in choice of equipment and installation.
  4. Calibration and Other Gases.-
  Gases used for calibrations, fuel and
combustion air (if required) are contained ia
compressed gaa cylinders. Preparation of
calibration gase* shall be done according to-
the procedure in Protocol No. 1, listed in     x
Reference &2. Additionally, the manufacturer
of the cylinder should provide a
recommended shelf life for each calibration
gas cylinder over which the concentration
does not change more than #2 percent from
the certified value. For calibration gas values
not generally available (i.e., organics
between 1 and 10 percent by  volume),
alternative methods for preparing calibration
gas mixtures, such as dilution systems, may
be used with prior approval of the
Administrator..
  Calibration gases usually consist of
propane in air or nitrogen and are determined
in terms of the span value. Organic
compounds other than propane can be used
following the above guidelines and making
the appropriate corrections for response
factor.
  4.1 /da/. A 40 percent Hi/60 percent He or
40 percent H./60 percent N«as mixture is
recommended to avoid an oxygen synergisin
affect that reportedly occurs when oxygen
amcentratioo varies significantly from a
nean value.
  43 Zero Gas. High purity air with less
than 0.1 parts per million by volume (ppmv)
of organic material (propane or carbon
                                                                                          * Morton of trade name* or specific products
                                                                                         ion not constitute endorsement by the
                                                                                         Environmental Protection Agency.
        HACK
 if Mum Mattuf ««•
                                                           I SytMm.

                                                              25A-10

-------
     Federal Register /  Vol. 4a  No.  161  / Thursday. August  18. 1983 / Rules  and Regulations
  equivalent) or less than 0.1 percent of the
  span value, whichever is greater.
   4J Law-level Calibration Gas. Anorganic
  calibration ga* with a concentration
  tqoivalent to 25 to 36 percent of the
  applicable span value
   4.4 Mid-level Calibration Gag. An organic
  calibration gas with a concentration
  equivalent to 45 to 55 percent of the
  applicable span value.
   4J High-level Calibration Gas. Pm
  organic calibration ga* with a concentration
  equivalent to 80 to 90 percent of the
  applicable span value.
   5. Measurement System Performance
 Specifications.
   5.1  Zero Drift. Let* than ±3 percent of
  die span value.
   &2  Calibration Drift. Leu than ±3
 percent of span value.
   i3  Calibration Error. Less than ±5-
 percent of the calibration gas value.
   8. Pretest Preparation*.
   0.1  Selection of Sampling Site. The
 location of the sampling rite is generally
 specified by the applicable regulation or
 purpose of the test; i.e- exhaust stack, inlet
 one. etc. The sample port shall be located at
 least L5 meters or 2 equivalent diameters
 (whichever is lees) upstream of the gas
 discharge to die atmosphere.
   &Z  Location of Sample Probe. Install the
 sample probe so that the probe is centrally
 located in the stack, pipe, or duct and is
 sealed tightly at die stack port connection.
   A3  Measurement System Preparation.
 Prior to die emission test, assemble die
 measurement systenVfollowing the
 manufacturer's written instructions in
 preparing the sample interlace and the
 organic analyzer. Make the system operable.
   FLA equipment can be calibrated for almost
 any range of total otganics concentrations.
 For high concentrations of organic* (> 1X1
 percent by volume as propane) modifications
 to most commonly available analyzers are
 necessary. One accepted method of
 equipment modification is to decrease the
 tax of die sample to the analyzer through the
 use of • smaller diameter sample capillary.
 Direct and oontnuioua measurement of
 organic concentration is a necessary
 consideration when determining any
 modification design.
  8.4  Calibration Error Test. Immediately
 prior to the test series, (within 2 hours of the
 start of the test) introduce zero gas and high-
 level calibration gas at the calibration valve
 assembly. Adjust die analyzer output to the
 appropriate levels, if necessary. Calculate the
 predicted response for die low-level and mid-
 •vel gases based on a linear response line
 between the. zero and high-level responses.
 Tien introduce low-level  and mid-level
 calibration gases successively to die        .
 measurement system. Record the analyzer
 responses for low-level and mid-level
 calibration gases and determine die
 differences between die measurement system
Ksponses and die predicted responses. These
 differences must be less than 5 percent of die
respective calibration gas value. If not. die
measurement system is not acceptable and
oust be replaced or repaired prior to testing.
No adjustments to the measurement system
shall be conducted after die calibration and
  before die drift check (Section 7.3). If
  adjustments are necessary before die
  completion of die test series, perform die drift
  checks prior to die required adjustments and
  repeat die calibration following die
  adjustments. If multiple electronic ranges are
  to be used, each additional range must be
  checked with a mid-level calibration gas to
  verify die multiplication factor.
   &S Response Tune Test Introduce zero
  gas into the measurement system at the
  calibration valve assembly. When die system
  output has stabilized, switch quickly to die
  high-level calibration gas. Record die time
  from die concentration change to die
  measurement system response equivalent to
  95 percent of die step change. Repeat die test
  three times and average die results.
   7. Emission Measurement Test
   7.1  Organic Measurement. Begin sampling
 at the start of die test period, recording time
 and any required process information as
 appropriate. In particular, note on die
 recording chart periods of process
 interruption or cyclic operation.
   73  Drift Determination. Immediately
 following die completion of die test period
 and hourly during die test period, reintroduce
 die zero and mid-level calibration gases, one
 at a time, to die measurement system at die
 calibration valve assembly. (Make no
 adjustments to die measurement system until
 after boUt die zero and calibration drift
 checks are made.) Record die analyzer
 response. If die drift values exceed die
 specified limits, invalidate die test results
 preceding dw check and repeat die test
 following corrections to die measurement
 system. Alternatively, recalibrate dw test
 measurement system as in Section 8.4 and
 report die results using both sets of
 calibration data (i.e., data determined prior to
 die test period and data determined following
 die test period).
   8. Organic Concentration Calculations.
   Determine die average organic
 concentration in terms of ppmv as propane  or
 other calibration gas. The average shall be
 determined by die  integration of die output
 recording over die  period specified in die
 applicable regulation.
   If result* are required in terms of ppmv as
 carbon, adjust measured concentrations using
 Equation 25A-1.
Eq.25A-l
Where:    *
Cc**Organic concentration as carbon, ppmv.
       Organic concentration as measured,
K= Carbon equivalent correction factor.
  K=2 for etiiane.
  K= 3 for propane.
  K=4 for butane.
  K= Appropriate response factor for other
    organic calibration gases.
  9. Bibliography.
  9.1   Measurement of Volatile Organic
Compounds — Guideline Series. U.S.
Environmental Protection Agency. Research
Triangle Park, N.C. Publication No. EPA-45O/
2-78-041. June 1978. p. 46-54.
  9.2   Traceability Protocol for Establishing
True Concentrations of Cases Used for
   3.1  Organic Concentration Analyzer. A
  flame ionization analyzer (FIA) capable of
  meeting or exceeding die specifications in
  this method.
   3.2  Sample Probe. Stainless steeL or
  equivalent, three-hole rake type. Sample
  holes shall be 4 mm in diameter or smaller
  and located at 16.7,50. and 83.3 percent of die
  equivalent stack diameter. Alternatively, a
  single opening probe may be used so that a
  gas sample is collected from die centrally
  located 10 percent area of die stack cross-
  section.                     ;
   3.3  Sample Line. Stainless steel or Teflon*
  tubing to transport die sample, gas to die
  analyzers. The sample line should be heated.
  if necessary, to prevent condensation in die
  line.
   3.4  Calibration Valve Assembly. A dine-
  way valve assembly to direct die zero and
  calibration gases to die analyzers is
  recommended. Otiier methods, such as quick-
  connect lines, to route calibration gas to die
  analyzers are applicable.
   3.5  Particulate Filter. An in-stack or an
  out-of-stack glass fiber-filter is recommended
  if exhaust gas paniculate loading is
  significant. An out-of-stack filter should be
  heated to prevent any condensation.
   34 Recorder. A atrip-chart recorder.
  analog computer, or digital recorder for
 recording measurement data. The minmram
 data recording requirement is one
 measurement value per minute. Note: This .
 method is often applied in highly explosive
 anas. Caution and can should be exercised
 in choice of equipment and installation.
   4. Calibration and Other Gases. *
   Gases used for calibrations, fuel, and
 combustion air (if required)-are contained in
 compressed gas cylinders. Preparation of
 calibration gases shall be done according to
 die procedure in Protocol No. 1. listed in
 Reference 9.2. Additionally, the manufacturer
 of die cylinder should  provide a
 recommended shelf life for each calibration
 gas cylinder over which die concentration
 does not change more  than #2 percent from
 die certified value. For calibration gas values
 not generally available (i.e.. organics
 between 1 and 10 percent by volume),
 alternative methods for preparing calibration
 gas mixtures, such as dilution systems, may
 be used with prior approval of die
 Administrator.
  Calibration gases usually consist of
 propane in air or nitrogen and are determined
 in terms of die span value. Organic
 compounds other than  propane can be used
 following die above guidelines and making
 die appropriate corrections for response
 factor.
  * 1  Fuel. A 40 percent H./60 percent He or
 10 percent H./60 percent N,gas mixture is
 recommended to avoid an oxygen synergism
 affect that reportedly occurs when oxygen
 concentration varies significantly from a
 nean value.
  43  Zero Gas. High purity air with less
than 0.1 parts per million by volume (ppmv)
of organic material (propane or carbon
  * Mention of trade name* or specific product*
loe» not constitute endorsement by the
Environmental Protection Agency.
                                                           25A-11

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Federal Register  /  Vol. 48,  No.  161  /  Thursday. August 18. 1983 /  Rules and Regulations
 equivalent) or less than 0.1 percent of the
 span value, whichever is greater.
   4.3  Low-level Calibration Gas. fat organic
 calibration gas with a concentration
 equivalent to 25 to 35 percent of the
 applicable span value.
   4.4  Mid^cvel Calibration Gas. Anorganic
 calibration gas with a concentration
 equivalent to 45 to 55 percent of the
 applicable spaa value.
   43  High-level Calibration Gas. An
 organic calibration gas with a concentration
 equivalent to 60 to 90 percent of the
 applicable span value.
   5. Measurement System Performance
 Specifications.
   &1  Zen Drift. Less than ±3 percent of
 the span value.
   &2 Calibration Drift. Less than ±3
 percent of span value.
   i3 Calibration Error. Less than ±5-
 percent of me calibration gas value.
   & Pretest Preparations.
   0.1 Selection of Sampling Site, the
 location of the sampling site is generally
 specified by the applicable regulation or
 purpose of the test; i.e., exhaust stack, inlet
 tee. etc.The sample port shall be located at
 least L5 meters or 2 equivalent diameters
 (whichever is less) upstream of the gas
 dischafge 19 the- atmosphere.
   O2 • Location of Sample Probe. Install the
 sample probe so that the probe is centrally
  located in the stack, pipe, or duct and is
  sealed tightly at the stack port connection.
   A3  Measurement System Preparation.
  Prior ta the emission teat asaemble the
  measurement system'following the
  Manufacturer's written instructions in
  preparing the sample interface and the
  organic analyzer. Make the system operable.
    FIA equipment can be calibrated for almost
  aioy mags of total oxganics concentrations.
.  For la^ concentration* of organic* (> 1.0
 . percent by volume as propane) modifications
  to moe* commonly available analyzers are
  necessary. One accepted method of
  equipment modification is to decrease the
  size of me sampk to the analyzer through the
  ueofismaller diameter sample capillary.
  Dteect and aanHmimn measurement of

  consideration when determining any
  64  Calibration Error Test Immediately
prior to me test series, (within 2 hours of the
start of me test) introduce zero gas and high-
level calibration gas at the calibration valve
«M«0ty. Adjast the analyzer output to the
appropriate levels, if necessary. Calculate the
pradictad response for the low-level and mid-
levai gases based on a Unear response line
between me zero and high-level responses.
then introduce low-level and mid-level
catibMtian gases successively to the
           t system. Record the analyzer
        i foiMuW level and mid-level
              i SJM deten&nte use*
                 i the measurement system
          Mind the predicted responses. These
              the teas than S percent of the
respective calibration gas value. If not the
mmsufMHent system is not acceptable and
must be replaced or repaired prior to testing.
No adjustments to the measurement system
shafl be conducted after the calibration and
                             before the drift check [Section 7.3). If
                             adjustments are necessary before the
                             completion of the test series, perform the drift
                             checks prior to the required adjustments and
                             repeat the calibration following the
                             adjustments. If multiple electronic ranges are
                             to be used,  each additional range must be
                             checked with a mid-level calibration gas to
                             verify the multiplication factor.
                               &S  Response Time Test. Introduce zero
                             gas into the measurement system at the
                             calibration valve assembly. When the system
                             output has stabilized, switch quickly to the
                             high-level calibration gas. Record the time
                             from the concentration change to the
                             measurement system response equivalent to
                             95 percent of the step change. Repeat the test
                             three times and average the results.
                               7. Emission Measurement Test
                               7.1  Organic Measurement. Begin sampling
                             at the start of the test period, recording time
                             and any required process information as
                             appropriate, hi particular, note on the
                             recording chart periods of process
                             interruption or cyclic operation.
                               72 Drift Determination. Immediately
                             following the completion of the test period
                             and hourly during the test period, reintroduce
                             the zero and mid-level calibration gases, one
                             at a time, to the measurement system at the
                             calibration valve assembly. (Make no
                             adjustments to the measurement system until
                             -after both the zero and calibration drift
                             checks are made.) Record the analyzer
                             response. If the drift values exceed the
                             specified limits, invalidate the teat results
                              preceding the check and repeat me test
                              following corrections to the measurement
                              system. Alternatively, recalibrate the test
                             measurement system as in Section 6.4 and
                             report the results using both sets of
                             calibration data (i.e., data determined prior to
                             the test period and data determined following
                             the test period).
                                8. Organic Concentration Calculations.
                                Determine the average organic
                              concentration in terms of ppmv as propane or
                              other calibration gas. The average shall be
                              determined by the integration of the output
                              recording over the period specified in the
                              applicable regulation.
                                If results are required in terms of ppmv as
                              carbon, adjust measured concentrations using
                              Equation 25A-1.
                              C.-KC...
                              Eq. 25A-1
                              Where:   -
                                  Organic concentration as carbon, ppmv.
                                     Organic concentration as measured,
                                  ppmv.
                              K=Carbon equivalent correction factor.
                                K-2 for ethane.
                                K=3 for propane.     4
                                K«4 for butane.
                                K=Appropriate response factor for other
                                  organic calibration gases.
                                9. Bibliography.
                                9.1   Measurement of Volatile Organic
                              Compounds—Guideline Series. US.
                              Environmental Protection Agency. Research
                              Triangle Park. N.C. Publication No. EPA-450/
                              2-78-041. June 1978. p. 40-54.
                                9.2   Traceability Protocol for Establishing
                              True Concentrations of Gases Used for
                                                                                     Calibration and Audits of Continuous Source
                                                                                     Emission Monitors (Protocol No. 1). U.S.
                                                                                     Environmental Protection Agency,
                                                                                     Environmental Monitoring and Support
                                                                                     Laboratory. Research Triangle Park. N.C.
                                                                                     June 1978.
                                                                                       9.3  Gasoline Vapor Emission Laboratory
                                                                                     Evaluation—Part 2. U.S. Environmental
                                                                                     Protection Agency, Office of Air Quality
                                                                                     Planning and Standards. Research Triangle
                                                                                     Park. N.C. EMB Report No. 75-GAS-6. August
                                                                                     1975.
                                                25A-12

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40 CFR Part 60,  Appendix  A
Final, promulgated
                   METHOD 25B  DETERMINATION OF TOTAL GASEOUS ORGANIC
                 CONCENTRATION USING A NONDISPERSIVE INFRARED ANALYZER
         1.  Applicability and Principle
              1.1  Applicability.  This method applies to the measurement of
         total gaseous organic concentration of vapors consisting primarily of
         alkanes.  (Other organic materials may be measured  using the general
         procedure in this method, the appropriate calibration  gas,  and an
         analyzer set to the appropriate absorption band.)   The concentration
         is expressed in terms of propane  (or other appropriate organic calibration
         gas) or in terms of carbon.
              1.2  Principle.  A gas sample  is extracted  from the source  through
         a heated sample line, if necessary, and  glass fiber filter  to  a  nondispersive
         infrared analyzer  (NDIR).   Results  are  reported  as  volume concentration
         equivalents of the calibration  gas  or as carbon  equivalents.
         2.   Definitions
              The terms and definitions  are  the  same  as  for Method  25A.
         3.   Apparatus  The apparatus  are  the  same as  for Method 25A with the
         exception of  the  following:
              3.1  Organic  Concentration Analyzer.  A nondispersive infrared
         analyzer designed  to  measure  alkane organics and capable of meeting or
         exceeding  the specifications  in this method.
         4.   Calibration  Gases
              The  calibration gases are the same as are required for Method 25A,
         Section 4.   No fuel  gas is required for an NDIR.
                                         25B-1

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5.  Measurement System Performance Specifications
     5.1   Zero Drift.   Less than ±3 percent of the span value.
     5.2   Calibration  Drift.   Less than ±3 percent of the span value.
     5.3   Calibration  Error.   Less than ±5 percent of the calibration
gas valve.
6.  Pretest Preparations
     6.1   Selection of Sampling Site.  Same as in Method 25A, Section  6.1.
     6.2   Location of  Sample Probe.  Same as  in Method 25A, Section  6.2.
     6.3   Measurement  System Preparation.  Prior to  the emission  test,
                                                                        i
assemble  the measurement system following the manufacturer's written
instructions in preparing the sample interface and the organic analyzer.
Make the  system operable.
     6.4   Calibration  Error Test.  Same as in Method 25A, Section 6.4.
     6.5   Response Time Test Procedure.  Same as in  Method 25A, Section  6.4.
7.  Emission Measurement Test Procedure
     Proceed with the  emission measurement immediately upon satisfactory
completion of the calibration.
     7.1   Organic Measurement.  Same as in Method 25A, Section 7.1.
     7.2  Drift Determination.  Same as in Method 25A, Section 7.2.
8.  Organic Concentration Calculations
     The calculations  are the same as  in Method 25A, Section  8.
9.  Bibliography
     The bibliography is the same as in Method 25A,  Section 9.
                                 25B-2

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Federal Register  /  Vol. 48.  No.  161 /  Thursday. August 18. 1983 / Rules  and  Regulations

                                     Method 25B—Determination of Total
                                     Gaaeoua Organic Concentration Us*no. a
                                     Nondispwrsiv* Infrared Analyzer
                                       1. Applicability and Principle.
                                       1.1  Applicability. This method applies to
                                     the measurement of total gaseous organic
                                     concentration of vapors consisting primarily
                                     of alkanes. (Other organic materials may be
                                     measured using the general procedure in this
                                     method, the appropriate calibration gas, and
                                     an analyzer set to the appropriate absorption
                                     band.) The concentration is expressed in
                                     terms of propane (or other appropriate
                                     organic calibration gas) or in terms of carbon.
                                       13  Principle.  A gas sample is extracted
                                     from the source through a heated sample line,
                                     if necessary, and glass fiber filter to a
                                     nondiffpersive infrared analyzer (NDIR).
                                     Results are reported as volume concentration
                                     equivalents of the calibration gas or as
                                     carbon equivalents.
                                       2. Definitions.
                                       The terms and definitions are the same as
                                     for Method 25A.
                                       3. Apparatus. The apparatus are the same
                                     as for Method 25A with the exception of the
                                     following:
                                       3.1   Organic Concentration Analyzer. A
                                     nondispenive infrared analyzer designed to
                                     measure alkane organics and capable of
                                     meeting or exceeding the specifications in
                                     this method.
                                       4.  Calibration Gases.
                                       The calibration gases are the same as are
                                     required for Method 25A, Section 4. No fuel
                                     gas is required for an NDIR.
                                        5. Measurement System Performance
                                     Specifications.
                                        5.1  Zero Drift Less than ±3 percent of
                                     the span value.                      «
                                        £2  Calibration Drift. Less than ±3
                                     percent of the span value.
                                        5.3  Calibration Error. Less than ±5
                                     percent of the calibration gas valve.
                                        8. Pretest Preparations.
                                        6.1  Selection of Sampling Site. Same as in
                                     Method 25A. Section 6.1.
                                        ft?  Location of Sampling Probe. Same as
                                      in Method 25A, Section 6.2.
                                        &3  Measurement System Preparation.
                                      Prior to the emission test assemble the
                                      measurement system following the
                                      manufacturer's written instructions in
                                      preparing the sample interface and the
                                      organic analyser. Make the system operable.
                                        6.4  Calibration Error Test Same as in
                                      Method 25A. Section 6.4.
                                        &5  Response Time Test Procedure. Same
                                       as in Method 25A, Section 6.4.
                                        7. Emission Measurement Test Procedure.
                                        Proceed with the emission measurement
                                       immediately upon satisfactory completion of
                                       the calibration.
                                         7.1  Organic Measurement. Same as in
                                       Method 25A. Section 7.1.
                                         7.2  Drift Determination. Same as in
                                       Method 25A. Section 7.2.
                                         a Organic Concentration Calculations.
                                         The calculations are the same as in Method
                                       25A, Section 8.
                                         9.' Bibliography.
                                         The bibliography is the same as in Method
                                       25A. Section 9.

                                                     25B-3

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40 CFR  Part 60, Appendix A
Final, promulgated
                 METHOD 27-DETERMINATION OF VAPOR TIGHTNESS OF GASOLINE
                       DELIVERY TANK USING-PRESSURE-VACUUM TEST
       1.   Applicability and Principle
            1.1  Applicability.   This method  is applicable  for  the determination
                                           !
       of vapor tightness of a gasoline delivery tank which is  equipped with
       vapor  collection  equipment.
            1.2  Principle.  Pressure and vacuum are applied alternately  to
       the compartments  of a gasoline delivery tank and the change  in pressure
       or vacuum is  recorded after  a  specified period of time.
       2.   Definitions  and Nomenclature
            2.1  Gasoline.  Any  petroleum distillate or petroleum distillate/
       alcohol blend having a  Reid  vapor  pressure of 27.6 kilopaseals or
       greater which is  used as  a fuel  for internal combustion engines.
             2.2  Delivery tank.   Any container, including associated pipes
       and  fittings, that is attached 'to  or forms a part of any truck, trailer,
        or railcar  used for the transport of gasoline.
             2.3   Compartment.   A liquid-tight division of a delivery tank.
             2.4  Delivery tank vapor collection equipment.  Any piping,
        hoses, and  devices on the delivery tank  used  to collect and route
        gasoline vapors either from the tank to  a  bulk terminal vapor control
        system or from a bulk plant or service station into the tank.
             2.5  Time period of  the pressure  or vacuum test (t).   The  time
        period of the  test, as specified  in  the appropriate regulation, during
        which the change  in pressure or vacuum is monitored, in minutes.
              2.6  Initial  pressure  (Pj).   The pressure applied to the delivery
        tank  at the  beginning  of the  static  pressure test,  as specified in the
        appropriate  regulation,  in  mm
                                         27-1

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     2.7  Initial  vacuum (V.).  The vacuum applied to the delivery
tank at the beginning of the static vacuum test, as specified In the
appropriate regulation, in mm O.
     2.8  Allowable pressure change ( p).  The allowable amount of
decrease in pressure during the static pressure test, within the time
period t, as specified in the appropriate regulation, in mm O.
     2.9  Allowable vacuum change  ( v).  The allowable amount of
decrease in vacuum during the static vacuum test* within the time
period t, as specified in the appropriate regulation, in mm H^O.
3.   Apparatus
     3.1  Pressure source.  Pump or compressed  gas cylinder of air or
Inert gas sufficient to  pressurize the delivery tank to  500 mm H20
above atmospheric  pressure.
     3.2  Regulator.   Low  pressure regulator for  controlling
pressurization of  the  delivery tank.
     3.3  Vacuum source.   Vacuum  pump capable of  evacuating the delivery
tank to 250 mm hUO below atmospheric pressure.
     3.4  Pressure-vacuum  supply  hose.
     3.5  Nanometer.   Liquid  manometer,  or  equivalent instrument,
capable of  measuring  up to 500 mm K,0 gauge pressure with  ±2.5 mm \LQ
 precision.
      3.6   Pressure-vacuum  relief  valves.  The  test apparatus  shall  be
 equipped  with an  in-line pressure-vacuum relief valve set  to  activate
 at 675 mm H«0 above  atmospheric pressure or 250 mm H«0  below atmospheric
 pressure, with a  capacity  equal to the  pressurizing or  evacuating
 pumps.
                               27-2

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     3.7  Test cap for vapor recovery hose.  This cap shall  have a tap
for manometer connection and a fitting with shut-off valve for connection
to the pressure-vacuum supply hose.
     3.8  Caps for liquid delivery hoses.
4-   Pretest Preparations
     4.1  Summary.  Testing problems may occur due to the presence of
volatile vapors and/or temperature fluctuations  inside the delivery
tank.  Under these conditions, it  is often  difficult to  obtain  a
stable initial pressure at the beginning of a test, and  erroneous test
results may occur.  To help prevent  this,  it  is  recommended  that,
prior to testing, volatile vapors  be removed  from the tank and  the
temperature  inside the tank be allowed  to  stabilize.  Because it is  not
always  possible  to attain completely these pretest conditions a provision
to ensure  reproducible  results  is included.  The difference in results
 for two consecutive  runs must meet the criterion in Sections 5.2.5 and
 5.3.5.  .
      4.2  Bnptying  of tank.  The delivery  tank  shall be emptied of all
 liquid.
      4.3  Purging of vapor.  As much as possible,  the delivery tank
 shall be purged of all volatile vapors by  any  safe, acceptable method.
 One method is to carry a load of  non-volatile  liquid  fuel,  such as
 diesel or heating oil,  immediately  prior  to  the test,  thus  flushing
 out all the volatile gasoline vapors.   A  second method is  to remove
 the volatile  vapors  by  blowing  ambient air into each tank  compartment
  for  at least  20 minutes.   This  second method is usually not as effective
  and  often causes stabilization problems,   requiring a much  longer time
  for stabilization .during the testing.
                                 27-3

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     4.4  Temperature stabilization.  As much as possible, the test
shall  be conducted under isothermal conditions.  The temperature of
the delivery tank should be allowed to equilibrate in the test environm
During the test, the tank should be protected from extreme environmenta
and temperature variability, such as direct  sunlight.
5.   Test Procedure
     5.1  Preparations.
     5.1.1  Open and close each dome cover.
     5.1.2  Connect static electrical ground connections  to  tank.
Attach the liquid delivery and vapor return  hoses,  remove the liquid
delivery elbows, and plug the liquid delivery fittings.   (Note:  The
purpose of testing the  liquid delivery  hoses is to  detect tears  or
holes that would allow  liquid leakage during a  delivery.  Liquid
delivery hoses  are not  considered  to be  possible sources  of  vapor
leakage, and thus, do not have to  be attached for a  vapor leakage
test.  Instead, a liquid delivery  hose  could be either visually  inspectc
or  filled with  water to detect any liquid leakage.)
      5.1.3  Attach the  test  cap  to the  end of the vapor recovery hose.
      5.1.4  Connect  the pressure-vacuum supply hose and the  pressure-
vacuum relief  valve  to  the  shut-off valve.  Attach a manometer to the
pressure tap.
      5.1.5  Connect  compartments of the tank internally to  each other
if possible.   If not possible, each compartment must be tested separate!
as if it were  an individual  delivery tank.
      5.2   Pressure test.
      5.2.1  Connect  the pressure source to the pressure-vacuum supply
 hose.
                                27-4

-------
     5.2.2  Open the shut-off valve in the vapor recovery hose cap.
Applying air pressure slowly, pressurize the tank to P^ the initial
pressure specified in the regulation.
     5.2.3  Close the shut-off valve and allow the  pressure in the
tank to stabilize, adjusting the  pressure  if necessary to maintain
pressure of P^.  When the pressure stabilizes, record the time and
initial pressure.
     5.2.4  At the end of t minutes, record the  time and final pressure.
     5.2.5  Repeat steps 5.2.2 through 5.2.4 until  the change in
pressure for two consecutive runs agrees within  ±12.5 nro FLO.  Calculate
the arithmetic average of the two results.
     5.2.6  Compare the average measured change  in  pressure to the
allowable pressure change, Ap, as specified  in the  regulation.   If the
delivery tank  does not satisfy the vapor tightness  criterion  specified
in the  regulation, repair the sources  of leakage, and  repeat  the
pressure test  until the criterion is met.
     5.2.7  Disconnect the  pressure  source from  the pressure-vacuum
supply  hose, and  slowly open the  shut-off valve  to  bring  the  tank to
atmospheric  pressure.
      5.3  Vacuum test.
      5.3.1   Connect the  vacuum source to the pressure-vacuum supply
hose.
      5.3.2   Open the shut-off valve in the vapor recovery hose cap.
 Slowly  evacuate'the tank to V^,  the initial vacuum specified in the
 regulation.

                                27-5

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     5.3.3  Close the shut-off valve and allow the pressure in the
tank to stabilize, adjusting the pressure if necessary to maintain a
vacuum of V..   When the pressure stabilizes, record the time and
Initial vacuum.
     5.3.4  At the end of t minutes, record the time and final vacuum.
     5.3.5  Repeat steps 5.3.2 through 5.3.4 until the change in
vacuum for two consecutive runs agrees within ±12.5 mm tU).  Calculate
the arithmetic average of the two results.
     5.3.6  Compare the average measured change in vacuum to the
allowable vacuum change, AV, as specified in the  regulation.  If the
delivery tank does not satisfy the  vapor tightness criterion specific
in the regulation, repair the sources of leakage, and repeat the
vacuum test until the criterion is  met.
     5.3.7  Disconnect the vacuum source from the pressure-vacuum
supply nose, and  slowly open the shut-off valve to bring the tank  to
atmospheric pressure.
     5.4  Post-test clean-up.  Disconnect all test equipment and
return the delivery tank to  its pretest condition.
6.   Alternative  Procedures
     6.1  The  pumping  of water  into the  bottom  of a  delivery  tank  is
                    *
an  acceptable  alternative  to the  pressure  source  described  above.
Likewise, the  draining  of  water out of the  bottom of a  delivery tank
may be substituted  for the vacuum source.   Note that some  of  the
 specific  step-by-step procedures  in the  method  must  be  altered  slight*
 to accommodate these different  pressure  and vacuum  sources.

                                 27-6

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     6.2  Techniques other than  specified  above  may be  used  for  purging
and pressurizing a delivery tank,  if  prior approval is  obtained  from
the Administrator.  Such approval  will  be  based  upon demonstrated
equivalency with the above method.
                                  27-7

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          Federal Register  / Vol. 48.  No.  161  / Thursday. August 1.8. 1983  /  Rules and Regulations
Method 27—Determination of Vapor
TlgMnaM of Gaaoftw Delivery Tank Using
Prs*sure-V»cuum Te*t
  1. Applicability and Principle.
  1.1  Applicability. This method U
applicable for the determination'of vapor
tightness of a gasoline delivery tank which it
•quipped with vapor collection equipment
  12  Principle. Pressure and vacuum are
applied alternately to the compartments of a
gasoline delivery tank and the change in
pressure or vacuum is recorded after a
specified period of time.
  2. Definitions and Nomenclature.
  2.1  Gasoline. Any petroleum distillate or
petroleum distillate/alcohol blend having a
Reid vapor pressure of 27.6 kilopaacals or
greater which is used as a fuel for internal
combustion engines.
  22  Delivery tank. Any container.
including associated pipes and fittings, that is
attached to or forms a part of any truck,
trailer, or railcar used for the transport of
  23 Comportment A liquid-tight division
 of a delivery teak.
  24 Delivery tank vapor collection
 equipment. Any piping, hoses, and devices on
 the denvery tank used to collect and route
 gasoline vapom either from the tank to a bulk
 terminal vapor control system or from a bulk
 plant or service station into the tank,
  25  Time period of the pressure or
 vocuum tart ft;. The time period of the teat as
 specified to the appropriate regulation, during
 which the change in pressure or vacuum is
 monitored, in minutes.
  20  totio/pressure/PJ. The pressure
 applied to the delivery tank at the beginning
 of the static pressure test, as specified in the
 appropriate regulation, in mm rW>.
   27  Initial vacuum (V& The vacuum
 apptied to the delivery tank at the beginning
 of the static vacuum test as specified in the
 appropriate regulation, in mm HiO.
   20  'Allowable pressure change ftp]. The
 allowable amount of decrease in pressure
 during the static pressure teat within the time
 period t as specified in the appropriate
 regulation, in mm IU>.
   29  Allowable vacuum change (&v). The
 allowable amount of decrease in vacuum
 during the static vacnum test within the time
 period t as specified in the appropriate
 regulation, in mm tU>.
   3. Apparatus.
   8J  Pressure source. Pump of compressed
 gas cylinder of air or inert gas sufficient to
 pressurize the delivery tank to 500 mm rM>
 above atmospheric pressure.
   3J  Regulator. Low pressure regulator for
 controlling pressurization of the delivery
 teak
   SJ  Vacuum source. Vacuum pump
 capable of evacuating the delivery tank to
 250 Dm HdO below atmosphetic pressure.
   3.4  Pressure-vacuum supply hose.
   3.5  Manometer. Liquid manometer, or
 equivalent instrument, capable of measuring
 up to 500 mm H»O gauge pressure with ±2.5
 mm H,O precision.
   3.6  Pressure-vacuum relief valves. The
 test apparatus shall be equipped with an in-
 line pressure-vacuum relief valve set to
 activate at 875 mm HtO above atmospheric
 pressure or 250 mm HiO below atmospheric
 pressure, with a capacity equal to the
 pressurizing or evacuating pumps.
   3.7  Test cap for vapor recovery hose. This
*cap shall have a tap for manometer
 connection and a fitting with shut-off valve
 for connection to the pressure-vacuum supply
 hose.
   3.8  Caps for liquid delivery hoses.
   4. Pretest Preparations.
   4.1  Summary. Testing problems may
 occur due to the presence of volatile vapors
 and/or temperature fluctuations inside the
 delivery tank. Under these conditions, it is
 often  difficult to obtain a stable initial
 pressure at the beginning of a test and
 erroneous test results may occur. To help
 prevent this, it is recommended that prior to
 testing, volatile vapors be removed from the
 tank and the temperature inside the tank be
 allowed to stabilize. Because tt is not always
 possible to attain completely these pretest
 conditions a provision to ensure reproducible
 results is included. The difference in results
 for two consecutive runs must meet the
 criterion in Sections &2£ and 5.3,5.
    4JZ Emptying of tank. The detivery tank
 shall  be emptied of all liquid.
    4.3 Purging of vapor. As much as possible.
 the delivery tank shall be purged of all
 volatile vapors by any safe, acceptable
 method. One  method is to cany a load of
 non-volatile liquid fuel such as. diesel or
 heating oil immediately prior to the test thus
 flushing out all the volatile gasoline vapors. A
 second method is to remove the volatile
 vapors by blowing ambient air into each tank
 compartment for at least 20 minutes. This
 second method is usually not as effective and
 often causes stabilization problems, requiring
 a much longer time for stabilization during
 the testing.
    4.4  Temperature stabilization. As much
 as possible, the test shall be conducted under
 isothermal conditions. The temperature of the
 detivery tank should be allowed to
 equilibrate in the test environment During
 the test the tank should be protected from
 extreme environmental and temperature
 variability, such as direct sunlight
    6. Test Procedure.
    5.1  Preparations.
    5.1.1.     Open and close each dome cover.
    5.13  Connect static electrical ground
 connections to tank. Attach the tiquid
 detivery and  vapor return hoses, remove the
 tiquid detivery elbows, and plug the tiquid
 delivery fittings.
    (Notsw—The purpose of testing the liquid
 detivery hoses is to detect tears or holes that
 would allow tiquid leakage during a detivery.
 Liquid detivery hoses are not considered to
 be possible sources of vapor leakage, and
 thus, do not have to be attached for a vapor
 leakage test  Instead, a tiquid detivery hose
   could be either visually inspected, or filled
   with water to detect any liquid leakage.)
     5.1.3  Attach the test cap to the end of the
   vapor recovery hose.
     5.1.4  Connect the pressure-vacuum supply
   hose and the pressure-vacuum relief valve to
   the shut-off valve. Attach a manometer to the
   pressure tap.
     5.L5  Connect compartments of the tank
   internally to each other if possible. If not
   possible, each compartment must be tested
   separately, as if it were an individual
   delivery tank.
     5.2 Pressure test
     5JL1  Connect the pressure source to the
   pressure-vacuum supply hose.
     5^2  Open the shut-off valve in the vapor
   recovery hose cap. Applying air pressure
   slowly, pressurize the tank  to Ph the  initial
   pressure specified in the regulation.
     5.2.3  Close the shut-off valve and allow
   the pressure hi the tank to stabilize, adjusting
   the pressure if necessary to maintain
   pressure of Pj. When the pressure stabilizes,
   record the time and initial pressure.
    5.2.4  At the end of t minutes, record the
   time and final pressure.
    &2£  Repeat steps S.ZZ through 5.2.4 until
   the change in  pressure for two consecutive  "
   runs agrees within ±1Z5 mm HW3. Calculate
   the arithmetic average of the two results.
    5.2.6  Compare me average measured
  change in pressure to the allowable pressure
  change. Ap, as specified in the regulation. If
  the detivery tank  does not satisfy the vapor
  tightness criterion specified in the regulation.
  repair the sources of leakage, and repeat the
  pressure test until the criterion is met
    5i7 Disconnect the pressure source from
  the pressure-vacuum supply hose, and slowly
  open the shut-off valve to bring the tank to
  atmospheric pressure.
    &3  Vacuum test
    5J.1  Connect tile vacuum source to the
  pressure-vacuum supply hose.
    5.3-2  Open  the shut-off valve in the vapor
  recovery hose cap. Slowly evacuate the tank
  to V,. the initial vacuum specified in the
  regulation.
   5.3J  Close  the shut-off valve and allow
  the pressure in- the tank to stabilize, adjusting
  the pressure if necessary to maintain a
 vacuum of V*. When the pressure stabilizes,
 record the time and initial vacuum.
   5.3.4 At the end of t minute* record the
 time and final vacuum.
   5.3.5 Repeat steps SJJ through &A4 until
 the change in vacuum for two consecutive
 runs agrees within $12£ mm fWD. Calculate
 the arithmetic average of the  two results.
   5.3.8 Compare the average measured
 change in vacuum to the allowable vacuum
 change, Ap, as specified in the regulation. If
 the delivery tank does not satisfy the vapor
 tightness criterion specified in the regulation.  -
 repair the sources of leakage, and repeat the
 vacuum test until the criterion is met
   5.3.7 Disconnect the vacuum source from
 the pressure-vacuum supply hose, and  slowly
 open the shut-off valve to bring the tank to
 atmospheric pressure.
  3.4  Pott-test clean-up. Disconnect all test
 equipment and return the detivery tank to ita
 pretest condition.
  8. Alternative Procedures.
  8.1   The pumping of water into the bottom
of a detivery tank is an acceptable
                                                                 27-8

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Federal Register  /  Vol.  48.  No.  161 /  Thursday,  August 18.  1983  /  Rules and Regulations
alternative to the pressure source described
above. Likewise, the draining of water out of
the bottom of a delivery tank may be
substituted for the vacuum source. Note that
some of the specific step-by-step procedures
in the method must be altered slightly to
accommodate these different pressure and
vacuum sources.
  &2 Techniques other than specified above
may be used for purging and pressurizing a
delivery tank, if prior approval is obtained
bom the Administrator. Such approval will
be based upon demonstrated equivalency
with the above method.
[FR Doc. SS-22MO Blad «-»-•* *« •!
                                                      27-9

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40 CFR Part  61, Appendix B
Final, promulgated
                     METHOD 106—DETERMINATION OF VINYL CHLORIDE
                                FROM STATIONARY SOURCES
         Introduction
              Performance of this method should not be attempted by persons
         unfamiliar with  the operation of a gas chromatograph (GC)  nor by those
         who  are  unfamiliar with source sampling, because knowledge beyond
         the  scope  of this presentation is required.   Care must be  exercised
         to prevent exposure of sampling personnel  to vinyl chloride,  a
         carcinogen.
         1.   Applicability and  Principle
              1.1   Applicability.   The method is applicable to the  measurement
         of vinyl chloride in stack gases from ethylene dichloride, vinyl
         chloride,  and  polyvinyl  chloride manufacturing, processes.   The method
         does not measure vinyl  chloride contained  in particulate matter.
              1.2   Principle.   An  integrated bag sample of stack gas containing
         vinyl chloride (chloroethene)  is subjected to GC analysis  using a flame
         ionization  detector (FID).
         2.   Range  and  Sensitivity
              This  method is designed  for the 0.1 to  50 ppm range.   However,
         common GC  instruments  are capable of detecting 0.02 ppm vinyl  chloride.
         With proper calibration,  the  upper limit may be extended as needed.
                                        106-1

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3.  Interferences
     The chromatographic columns and the corresponding operating
parameters herein described normally provide an adequate resolution
of vinyl chloride; however, resolution interferences may be encountered
on some sources.  Therefore, the chromatograph operator shall select
the column and operating parameters best suited to his particular
analysis requirements, subject to the approval of the Administrator.
Approval is automatic, provided that the tester produces confirming
data through an adequate supplemental analytical technique, such as
analysis with a different column or GC/mass spectroscopy, and has the
data available for review by the Administrator.
4.  Apparatus
     4.1  Sampling (see Figure 106-1).  The sampling train consists of
the following components:
     4.1.1  Probe.  Stainless steel, Pyrex glass, or Teflon tubing
(as stack temperature permits) equipped with a glass wool plug to
remove particulate matter.
     4.1.2  Sample Lines.  Teflon, 6.4-mm outside diameter, of
sufficient length to connect probe to bag.  Use a new unused piece for
each series of bag samples that constitutes an emission test, and
discard upon completion of the test.
     4.1.3  Quick Connects.  Stainless steel,  male (2)  and female (2),
with ball checks (one pair without), located as shown in  Figure 106-1.
     4.1.4  Tedlar Bags.   50- to 100-liter capacity,  to contain sample.
Aluminized Mylar bags may be used if the samples are analyzed within
24 hours of collection.
                               106-2

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     4.1.5  Bag Containers.  Rigid leak-proof containers for sample
bags, with covering to protect contents from sunlight.
     4.1.6  Needle Valve.  To adjust sample flow rates.
     4.1.7  Pump.  Leak-free, with minimum of 2-liter/min capacity.
     4.1.8  Charcoal Tube.  To prevent admission of vinyl chloride
and other organics to the atmosphere in the vicinity of samplers.
     4.1.9  Flowmeter.  For observing sampling flow rate; capable
of measuring a flow range from 0.10 to 1.00 liter/min.
     4.1.10  Connecting Tubing.  Teflon, 6.4-mm outside diameter, to
assemble sampling train (Figure 106-1).
     4.1.11  Tubing Fittings and Connectors.  Teflon or stainless steel,
to assemble sampling train.
     4.2  Sample Recovery.  Teflon tubing, 6.4-mm outside diameter, to
connect bag to GC sample loop for sample recovery.  Use a new unused
piece for each series of bag samples that constitutes an emission test,
and discard upon conclusion of analysis of those bags.
     4.3  Analysis.  The following equipment is required:
     4.3.1  Gas Chromatograph.  With FID, potentiometric strip chart
recorder and 1.0- to 5.0-ml heated sampling loop in automatic sample
valve.  The chromatographic system shall be capable of producing a
response to 0.1-ppm vinyl chloride that is at least as great as the
average noise level.  (Response is measured from the average value of
the base line to the maximum of the wave form, while standard operating
conditions are in use.)
                               106-3

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     4.3.2  Chromatographic Columns.   Columns as listed below.  The
analyst may use other columns provided that the precision and accuracy
of the analysis of vinyl  chloride standards are not impaired and he
has available for review information confirming that there is adequate
resolution of the vinyl  chloride peak.  (Adequate resolution is defined
as an area overlap of not more than 10 percent of the vinyl chloride
peak by an interferent peak.  Calculation of area overlap is
explained in Appendix C,  Procedure 1:  "Determination of Adequate
Chromatographic Peak Resolution.")
     4^.2.1  Column A.   Stainless steel, 2.0 m by 3.2 nm, containing
80/100-mesh Chromasorb 102.
     4.3.2.2  Column B.   Stainless steel, 2.0 m by 3.2 mm, containing
20 percent GE SF-96 on 60/80-mesh Chromasorb P AW; or stainless steel,
1.0 m by 3.2 mm containing 80/100-mesh Porapak T.  Column B is required
as a secondary column if acetaldehyde is present.  If used, column B
is placed after column A.  The combined columns should be operated at
120° C.
     4.3.3  Flowmeters (2).  Rotameter type, 100-ml/min capacity, with
flow control valves.
     4.3.4  Gas Regulators.  For required gas cylinders.
     4.3.5  Thermometer.   Accurate to 1° C, to measure temperature of
heated sample loop at time of sample injection.
     4.3.6  Barometer.  Accurate to 5 mm Hg, to measure atmospheric
pressure around GC during sample analysis.
     4.3,7  Pump.  Leak-free, with minimum of 100-ml/min capacity.
                               106-4

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     4.3.8  Recorder.  Strip chart type, optionally equipped with
either disc or electronic integrator.
     4.3.9  Planimeter.  Optional, in place of disc or electronic
integrator on recorder, to measure chromatograph peak areas.
     4.4  Calibration.  Sections 4.4.2 through 4.4.4 are for the
optional procedure in Section 7.1.
     4.4.1  Tubing.  Teflon, 6.4-mm outside diameter, separate pieces
marked for each calibration concentration.
     4.4.2  Tedlar Bags.  Sixteen-inch-square size, with valve;
separate bag marked for each calibration concentration.
     4.4.3  Syringes.  0.5-ml and 50-yl, gas tight, individually
calibrated to dispense gaseous vinyl chloride.
     4.4.4  Dry Gas Meter, with Temperature and Pressure Gauges.
Singer model DTM-115 with 802 index, or equivalent, to meter nitrogen
in preparation of standard gas mixtures, calibrated at the  flow rate
used to prepare standards.
5.  Reagents
     Use only reagents  that are of  chromatograph grade.
     5.1  Analysis.   The  following  are  required for analysis.
     5.1.1  Helium or Nitrogen.   Zero grade,  for chromatographic
carrier gas.
     5.1.2  Hydrogen.   Zero  grade.
     5.1.3  Oxygen or Air.   Zero  grade, as required  by the  detector.
     5.2  Calibration.   Use one of  the  following options:   either
5.2.1  and 5.2.2,  or  5.2.3.
                                106-5

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     5.2.1  Vinyl Chloride.  Pure vinyl  chloride  gas  certified  by  the
manufacturer to contain a minimum of 99.9  percent  vinyl chloride,
for use in the preparation of standard gas mixtures in Section  7.1.
If the gas manufacturer maintains a bulk cylinder  supply of  99.9+
percent vinyl chloride, the certification  analysis may have  been
performed on this supply rather than on  each gas cylinder  prepared
from this bulk supply.  The date of gas  cylinder preparation and the
certified analysis must have been affixed  to the cylinder  before
shipment from the gas manufacturer to the  buyer.
     5.2.2  Nitrogen.  Zero grade, for preparation of standard  gas
mixtures as described in Section 7.1.
     5.2.3  Cylinder Standards (3).   Gas mixture standards (50-, 10-,
and 5-ppm vinyl chloride in nitrogen cylinders).  The tester may use
cylinder standards to directly prepare a chromatograph calibration
curve as described in Section 7.2.2, if  the following conditions are
met:   (a)  The manufacturer certifies the gas composition with an
accuracy of +3 percent or better (see  Section 5.2.3.1).   (b) The
manufacturer recommends a maximum shelf life over which the gas
concentration does not change by greater than +5 percent from the
certified, value,   (c) The manufacturer affixes the date of gas cylinder
preparation, certified vinyl  chloride  concentration,  and recommended
maximum shelf life to the cylinder before shipment to  the buyer.
     5.2.3.1  Cylinder Standards Certification.   The manufacturer
shall certify the concentration  of vinyl  chloride in nitrogen in each
cylinder by (a) directly analyzing each  cylinder and  (b)  calibrating
                               106-6

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his analytical procedure on the day of cylinder analysis.  To calibrate
his analytical procedure, the manufacturer shall use, as a minimum, a
three-point calibration curve.  It is recommended that the manufacturer
maintain (1) a high-concentration calibration standard (between 50 and
100 ppm) to prepare his calibration curve by an appropriate dilution
technique and (2) a low-concentration calibration standard (between 5
and 10 ppm) to verify the dilution technique used.   If the difference
between the apparent concentration read from the calibration curve and
the true concentration assigned to the low-concentration calibration
standard exceeds 5 percent of the true concentration, the manufacturer
shall determine the source of error and correct it,  then repeat the
three-point calibration.
     5.2.3.2  Verification of Manufacturer's Calibration Standards.
Before using a standard, the manufacturer shall verify each calibration
standard (a) by comparing it to gas mixtures prepared (with 99 mole
percent vinyl chloride) in accordance with the procedure described in
Section 7.1 or (b) calibrating it against vinyl chloride cylinder
Standard Reference Materials (SRM's) prepared by the National Bureau
of Standards, if such SRM's are available.  The agreement between the
initially determined concentration value and the verification
concentration value must be within +5 percent.  The  manufacturer must
reverify all calibration standards on a time interval consistent with
the shelf life of the cylinder standards sold.
                                 106-7

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     5.2.4  Audit Cylinder Standards (2).  Gas mixture standards
with concentrations known only to the person supervising the
analysis of samples.  The audit cylinder standards shall be
identically prepared as those in Section 5.2.3 (vinyl chloride in
nitrogen cylinders).  The concentrations of the audit cylinders
should be:  one low-concentration cylinder in the range of 5 to
20 ppm vinyl chloride  and one high-concentration cylinder in the
range of 20 to 50 ppm.  When available, the tester may obtain audit
cylinders by contacting:  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:  (a) the gas manufacturer certifies the audit
cylinders as described in Section 5.2,3.1, and (b) the gas
manufacturer obtains an independent analysis of the audit cylinders
to verify this analysis.  Independent analysis is defined here to
mean analysis performed by an individual different 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
complete and acceptable when the independent analysis
concentration is within +5 percent of the gas manufacturer's
concentration.
                               106-8

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6.  Procedure
     6.1  Sampling.  Assemble the  sample  train as  shown  in Figure 106-1.
A bag leak check should have been  performed  previouly according to
Section 7.3.2.  Join the quick connects as illustrated,  and determine
that all connections between the bag and  the probe are tight.  Place
the end of the probe at the centroid of the  stack  and start the pump
with the needle valve adjusted to  yield a flow that will fill over
50 percent of bag volume in the specified sample period.  After
allowing sufficient time to purge  the  line several  times, change the
vacuum line from the container to  the  bag and evacuate the bag until
the rotameter indicates no flow.   Then reposition  the sample and
vacuum lines and begin the actual  sampling,  keeping the  rate propor-
tional to the stack velocity.  At  all  times, 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.  Protect the bag
container from sunlight.
     6.2  Sample storage.  Keep the sample bags out of direct sunlight.
When at all possible, analysis is  to be performed  within 24 hours, but
in no case in excess of 72 hours of sample collection.   Aluminized
Mylar bag samples must be analyzed within 24 hours.
     6.3  Sample Recovery.  With a new piece of Teflon tubing
identified for that bag, connect a bag inlet valve to the gas
chromatograph sample valve.  Switch the valve to receive gas from the
bag through the sample loop.  Arrange  the equipment so the sample gas
                                106-9

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passes from the sample valve to 100-ml/min rotameter with  flow control
valve followed by a charcoal tube and a 1-in. H^O pressure gauge.
The tester may maintain the sample flow either by a vacuum pump or
container pressurization if the collection bag remains in  the rigid
container.  After sample loop purging is ceased, allow the pressure
gauge to return to zero before activating the gas sampling valve.
     6.4  Analysis.  Set the column temperature to 100° C  and the
detector temperature to 150° C.  When optimum hydrogen and oxygen flow
rates have been determined, verify and maintain these flow rates
during all chromatography operations.  Using zero helium or nitrogen
as the carrier gas, establish a flow rate in the range consistent
with the manufacturer's requirements for satisfactory detector
operation.  A flow rate of approximately 40 ml/min should  produce
adequate separations.  Observe the base line periodically and determine
that the noise level has stabilized and that base Tine drift has
ceased.  Purge the sample loop for 30 seconds at the rate of
100 ml/min, shut off flow,  allow the sample loop pressure to reach
atmospheric pressure as indicated by the H20 manometer, then activate
the sample valve.  Record the injection time (the position of the
pen on the chart at the time of sample injection),  sample number,
sample loop temperature, column temperature,  carrier gas flow rate,
chart speed, and attenuator setting.   Record the barometeric pressure.
From the chart, note the peak having the retention  time corresponding
to vinyl chloride as determined in Section 7.2.1.   Measure the vinyl
chloride peak area, A^, by  use of a disc integrator,  electronic
                               106-10

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 integrator, or a  planimeter.  Measure and record  the peak heights,
 Hm.  Record Am and retention time.  Repeat the  injection at
 least two times or until two consecutive values for the total area
 of the vinyl chloride peak do not vary more than  5 percent.  Use the
 average value for the these two total areas to compute the bag
 concentration.
     Compare the ratio of Hm to Am for the vinyl chloride sample with
 the same ratio for the standard peak that is closest in height.  If
 these ratios differ by more than 1C percent, the vinyl  chloride peak
may not be pure (possibly acetaldehyde is present) and  the secondary
column should  be employed (see Section 4.3.2.2).
     6.5  Determination of Bag Water Vapor Content.  Measure the
ambient temperature and barometric pressure near the bag.   From a
water saturation vapor pressure table, determine and record the water
vapor content of the bag as a decimal  figure.   (Assume  the relative
 humidity to be 100 percent unless a lesser value is known.)
7.  Preparation of Standard Gas Mixtures, Calibration,  and Quality
Assurance
     7.1  Preparation of Vinyl Chloride Standard Gas Mixtures.
 (Optional Procedure—delete if cylinder standards are used.)  Evacuate
 a 16-inch square Tedlar bag that has passed a leak check (described in
 Section 7.3.2) and meter in 5.0 liters of nitrogen.  While the bag is
 filling, use the 0.5-ml syringe to inject 250 yl  of 99.9+ percent
 vinyl chloride gas through the wall of the bag.   Upon withdrawing the
                                 106-11

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syringe, immediately cover the resulting hole with a piece of adhesive
tape.  The bag now contains a vinyl chloride concentration of 50 ppm.
In a like manner use the 50 ul syringe to prepare gas mixtures having
10- and 5-ppm vinyl chloride concentrations.  Place each bag on a
smooth surface and alternately depress opposite sides of the bag 50
times to further mix the gases.  These gas mixture standards may be
used for 10 days from the date of preparation, after which time new
gas mixtures must be prepared.  (Caution:  Contamination may be a
problem when a bag is reused if the new gas mixture standard is a lower
concentration than the previous gas mixture standard.)
     7.2  Calibration.
     7.2.1  Determination of Vinyl Chloride Retention Time.  (This
section can be performed simultaneously with Section 7.2.2.)  Establish
chromatograph conditions identical with those in Section 6.4 above.
Determine proper attenuator position.  Flush the sampling loop with
zero helium or nitrogen and activate the sample valve.  Record the
injection time, sample loop temperature, column temperature, carrier
gas  flow rate, chart speed, and attenuator setting.  Record peaks and
detector responses that occur  in  the absence of vinyl chloride.
Maintain conditions with the equipment plumbing arranged identically
to Section 6.3, and flush the  sample loop for 30 seconds at the rate
of 100 ml/min with one of the  vinyl chloride calibration mixtures.  Then
activate the sample valve.  Record the injection time.  Select the peak
that corresponds to vinyl chloride.  Measure the distance on the chart
from the injection time to the time at which the peak maximum occurs.
                                106-12

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This quantity divided by the chart speed is defined as the retention
time.  Since other organics may be present in the sample, positive
identification of the vinyl chloride peak must be made.
     7.2.2  Preparation of Chromatograph Calibration Curve.  Make a
GC measurement of each gas mixture standard (described
in Section 5.2.3 or 7.1) using conditions identical with those listed
in Sections 6.3 and 6.4.  Flush the sampling loop for 30 seconds at
the rate of 100 ml/min with one of the standard mixtures, and activate
the sample valve.  Record the concentration of vinyl chloride injected
(Cc), attenuator setting, chart speed, peak area, sample loop
temperature, column temperature, carrier gas flow rate, and retention
time.  Record the barometric pressure.  Calculate A , the peak area
multiplied by the attenuator setting.  Repeat until two consecutive
injection areas are within 5 percent, then plot the average of those
two values versus C .  When the other standard gas mixtures have been
similarly analyzed and plotted, draw a straight line through the
points derived by the least squares method.  Perform calibration daily,
or before and after the analysis of each emission test set of bag
samples, whichever is more frequent.  For each group of sample analyses,
use the average of the two calibration curves which bracket that group
to determine the respective sample concentrations.  If the two
calibration curves differ by more than 5 percent from their mean value,
then report the final results by both calibration curves.
                                106-13

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     7.3  Quality Assurance.
     7.3.1  Analysis Audit.  Immediately after the preparation of
the calibration curve and prior to the sample analyses, perform the
analysis audit described in Appendix C, Procedure 2:  "Procedure for
Field Auditing GC Analysis."
     7.3.2  Bag Leak Checks.  Checking of bags for leaks is required
after bag use and strongly recommended before bag use.  After each
use, connect a water manometer and pressurize the bag to
5 to 10 cm H^O (2 to 4 in. H20).  Allow to stand for 10 min.  Any
displacement in the water manometer indicates a leak.  Also, check
the rigid container for leaks in this manner.  (Note:  An alternative
leak check method is to pressurize the bag to 5 to 10 cm hLO and allow
it to stand overnight.  A deflated bag indicates a leak.)  For each
sample bag in its rigid container, place a rotameter in line between
the bag and the pump inlet.  Evacuate the bag.  Failure of the
rotameter to register zero flow when the bag appears to be empty
indicates a leak.
8.  Calculations
     8.1  Determine the sample peak area, A , as follows:

                              A  = A  A                   Eq.  106-1
                                       f
Where:
        »  Measured peak area.
        =  Attenuation factor.
                               106-14

-------
     8.2  Vinyl Chloride Concentrations.  From the calibration
curves described in Section 7.2.2, determine the average concentration
value of vinyl chloride, C , that corresponds to A , the sample peak
                          c        f               c
area.  Calculate the concentration of vinyl chloride in the bag,
CK, as follows:
                                    CcPrTi
                                                          ^ 106'2
Where:
     P   -  Reference pressure, the laboratory pressure recorded
            during calibration, mm Hg.
     T.  =  Sample loop temperature on the absolute scale at the
            time of analysis, °K.
     P. • =  Laboratory pressure at time of analysis, mm Hg.
     T   =  Reference temperature, the sample loop temperature
            recorded during calibration,  °K.
     B .  =  Water vapor content of the bag sample, as analyzed.
      wb
                                 106-15

-------
9.  Bibliography
     1.  Brown,  D.W.,  E.W.  Loy,  and M.H.  Stephenson.   Vinyl Chloride
Monitoring Near  the B,  F.  Goodrich Chemical Company in Louisville,
KY.  Region IV,  U.S. Environmental Protection Agency, Surveillance
and Analysis Division,  Athens,  GA.  June 24, 1974.
     2.  G.D. Clayton and Associates.  Evaluation of a Collection and
Analytical Procedure for Vinyl Chloride in Air.  U.S. Environmental
Protection Agency,  Research Triangle Park, N.C.  EPA Contract
No. 68-02-1408,  Task Order No. 2, EPA Report No. 75-VCL-l.
December 13, 1974.
     3.  Midwest Research Institute.  Standardization of Stationary
Source Emission  Method for Vinyl Chloride.  U.S. Environmental
Protection Agency,  Research Triangle Park, N.C.  Publication
No. EPA-600/4-77-026.  May 1977.
     4.  Scheil, G. and M.C. Sharp.  Collaborative Testing of EPA
Method 106 (Vinyl Chloride) that Will Provide for a Standardized
Stationary Source Emission Measurement Method.  U.S. Environmental
Protection Agency,  Research Triangle Park, N.C.  Publication
No. EPA 600/4-78-058.  October 1978.
                               106-16

-------
FILTER (GLASS WOOL)

             ,PR03E
   TEFLON
/SAMPLE LINE
VACUUM LINE
    STACK WALL
     FLOW METER
                    BALL
                    CHECKS
        QUICK
       CONNECTS
    riJ"AL\fL
    ^1 •        I _i ^
                   MO BALL
                   CHECKS
               * *^ ^  ,
               CO J
                         TEQLAR OR
                         ALUMINIZEQ
                         MYLAR BAG
                           RIGID LEAK-PROOF
                              CONTAINER
                                                PUMP
    Figure 106-1. Iniegrated-bag sampling train.  (Mention of trade names
    or specific products does not constitute endorsement by the Environ-
    mental Protection Agency.)
                     106-17

-------
         Federal  Register / Vol  47. No. 173 / Tuesday.  September 7. 1932 / Rules  and Regulations
                       i of Vtay I Chloride
            i of this method should not be
•tempted by persons unfamiliar with the
operation of • ga* chromatograph (GC) nor
by those woo «re unfamiliar with source
Mooting, became knowledge beyond the
scope of this presentation is required. Care
mutt be exercised to prevent exposure of
sampling personnel to vinyl chloride, a
carcinogen.

1. Applicability and Principle
  1.1  Applicability. The method is
   nicable to the measurement of vinyl
      " t in stack gaaes from ethylene
dichloride. vinyl chloride, and polyvinyl
chloride manufacturing processes. The
method does not measure vinyl chloride
contained in particulate matter.
  1.2   Principle. An integrated bag sample of -
stack gas containing vinyl chloride
(chloroethene) is subjected to GC analysis
•using a flame ionization detector (FID).

2. Range and Sensitivity
  This method is designed for the 0.1 to SO
ppm range. However, common GC
instruments are capable of detecting 0.02 ppm
vinyl  chloride. With proper calibration, the
upper limit may be extended as needed.

3. Interferences
  The chromatographic columns and the
corresponding operating parameters herein
described normally provide an adequate
resolution of vinyl chloride; however,
resolution interferences may be encountered
on some sources. Therefore, the
chromatograph operator shall select the
column and operating parameters best suited
to his particular analysis requirements.
subject to the approval of the Administrator.
Approval is automatic provided that the
tester produces confirming data through an
adequate supplemental analytical technique,
such as analysis with a different column or
GC/mass spectroscopy. and has the data
available for review by the Administrator.

4. Apparatus
  4.1  Sampling (see Figure 108-1). The
sampling train consists of the following
components:
  4.1.1  Probe. Stainless steel Pyrex glass, or
Teflon tubing (as stack temperature permits)
equipped with or glass wool plug to remove
particulate matter.
  4.1.2  Sample Lines. Teflon. 6.4-mm outside
diameter, of sufficient length to connect
probe to bag. Use a new unused piece for
each  series of bag samples that constitutes an
emission test and discard upon completion of
the test
  4.1.3 Quick Connects. Stainless steel.
male (2) and female (2). with ball checks (one
pair without).'located as shown in Figure 106-
1.
  4.1.4 Tedlar Bags. 50- to 100-liter capacity,
to contain sample. Aluminized Mylar bags   -
may be used if the samples are analyzed
within 24 hours of collection.
  4.1.5 Bag Containers. Rigid leak-proof
containers for sample bags, with covering to
protect contents from sunlight
  4.1.6 Needle Valve. To adjust sample flow
rates.
  4.1.7 Pump. Leak-free, with minimum of 2-
liter/min capacity.
  4.13 Charcoal Tube. To prevent
admission of vinyl chloride and other
organics to the atmosphere in the vicinity of
samplers.
  4.1.9. Flowmeter. For observing sampling
 flow rate: capable of measuring a flow range
 from 0,10 to 1.00 liter/min.
  4.1.10  Connecting Tubing. Teflon. 6.4-mm
 outside diameter, to assemble sampling train
 (Figure 106-1).
   4.1.11  Tubing Fittings and Connectors.
 Teflon or stainless steel, to assemble
 sampling train.
   4.2  Sample Recovery. Teflon tubing, b.4-
 mm outside diameter, to connect bag to CC
 sample loop for sample recovery. Use a new
 unused piece for each series of bag samples
 that constitutes an emission test, and discard
 upon conclusion of analysis of those bags.
   4.3  Analysis. The following equipment is
 required:
   4.3.1   Gas Chromatograph. With FID,
 potentiometric strip chart recorder and 1.0- to
 5.0-ml heated sampling loop in automatic
 sample valve. The chromatographic system
 shall be capable of producing a response to
 0.1-ppm vinyl chloride that is at least as great
 as the average noise level. (Response is
 measured from the average value of the base
 line to the maximum of the  wave form, while
 standard operating conditions are in use.]
   4.3.2   Chromatographic Columns. Columns
 as listed below. The analyst may use other
 columns provided that the precision and
 accuracy of the analysis of vinyl chloride
 standards are not impaired and he has
 available for review information confirming
 that there is adequate resolution of the vinyl
 chloride peak. (Adequate resolution is
 defined as an area overlap  of not more than
 10 percent of the vinyl chloride peak by an
 interferent peak. Calculation of area overlap
 is explained in Appendix C, Procedure 1:
 "Determination of Adequate
 Chromatographic Peak Resolution."]
   4.3.2.1 Column A. Stainless steel. 2.0 m by
 3.2 nun. containing 80/100-mesh Chromasorb
 102.
   4-3-2 Z Column B. Stainless steel 2.0 m by
 3.2 mm. containing 20 percent GE SF-96 on
 eO/80-mesh Chromasorb P AW; or stainless
 steel 1.0 m by 3.2 mm containing 80/100-
 mesh Porapak T. Column B is required as a
 secondary column if acetaldehyde is present.
 If used,  column B is placed after column A.
 The combined columns should be operated at
 120*C
   4.3.3  Flowmeters (2).  Rotameter type, 100-
 ml/min capacity, with flow control valves.
•   4.3.4  Gas Regulators. For required gas
 cylinders.
   4.3.5  Thermometer.'Accurate to 1* C, to
 measure temperature of heated sample loop
 at time of sample injection.
   4.3.6  Barometer. Accurate to 5 mm Hg. to „
 measure atmospheric pressure around GC
 during sample analysis.
   4.3.7  Pump. Leak-free, with minimum of
 lOO-ral/min capacity.
   4.3.8  Recorder. Strip chart type, optionally
 equipped with either disc or electronic
 integrator.
   4.3.9  Planimeter. Optional, in place of disc
 or electronic integrator on recorder, to
 measure chromatograph peak areas.
   4.4 Calibration. Sections 4.4.2 through
 4.4.4 are for the optional procedure in Section
 7.1.
   4.4:1  Tubing. Teflon. 6.4-mm outside
 diameter, separate pieces marked for each
 calibration concentration.
   4.4.2  Tedlar Bags. Slxteen-inch-square
 size, with valve; separate bag marked for
 each calibration concentration.
   4.4.3  Syrings. 0.5-ml and 50-pl. gas tight.
 individually calibrated to dispense gaseous
 vinyl chloride.
                                                          106-18

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            Federal Register  /  Vol.  47. No. 173  / Tuesday.  September 7. 1982  /  Rules and Regulations
   4.4.4  Dry Gas Meter, with Temperature
 and Pressure Gauges. Singer model DTM-115
 with 802 index or equivalent to meter
 nitrogen in preparation of standard gas
 mixtures, calibrated at the flow rate used to
 prepare standards.

 5. Reagents
   Use only reagents that are of  ,
 chromatograph grade.
   5.1  Analysis. The following are required
 for analysis.
   5.1.1  Helium or Nitrogen. Zero grade, for
 chromatographic carrier gas.
   5.1.2  Hydrogen. Zero grade.
   5.1.3  Oxygen or Air. Zero grade, as
 required by the detector.
   5.2  Calibration. Use one of the following
 options: either 5.2.1 and 5.2A or 5.2.3.
   5.2.1  Vinyl Chloride. Pure vinyl chloride
 gas certified by the manufacturer to contain a
 minimum of 99.9 percent vinyl chloride, for
 use in the preparation of standard gas  -
 mixtures in Section 7.1. If the gas
 manufacturer maintains a bulk cylinder
 supply of 99.9+ percent vinyl chloride, the
 certification analysis may have been
 performed on this supply rather than on each
 fas cylinder prepared from this bulk supply.
 The date of gas cylinder preparation and the
 certified analysis must have been affixed to
 me cylinder before shipment from the gat
 manufacturer to the buyer.
   O2  Nitrogen. Zero grade, for preparation
 of standard gas mixtures as described in
 Section 7.1.
   Si3  Cylinder Standards (3). Gas mixture
 standards (50-. 10-. and 5-ppm vinyl chloride
 in nitrogen cylinders). The tester may use
 cylinder standards to directly prepare  a
 chromatograph calibration curve as
 described in Section 7.2-2. if the following
 conditions are met (a) The manufacturer
 certifies the gas composition with an
 accuracy of ±3 percent or better (see Section
 5£3.1). (b) The manufacturer recommends a
 maximum shelf life over which the gas
 concentration does not change by greater
 man ±5 percent from the certified value, (c)
 The manufacturer affixes the date of gas
 cylinder preparation, certified vinyl chloride
 concentration, and recommended maximum
 shelf life to the cylinder before shipment to
 me buyer.
  SA3.1  Cylinder Standards Certification.
 The manufacturer shall certify the
 concentration of vinyl chloride in nitrogen in
 seen cylinder by (a) directly analyzing each
• cylinder and (b) calibrating his analytical
 procedure on the day  of cylinder analysis. To
 calibrate his analytical procedure, the
 manufacturer shall use, as a minimum, a
 three-point calibration curve. It is
 recommended that the manufacturer maintain
 (1) a high-concentration calibration standard
 (between 50 and 100 ppm) to prepare his
 calibration curve by an appropriate dilution
 technique and (2) a low-concentration
 calibration standard (between 5 and 10 ppm)
 to verify the dilution technique used. If the
 difference between the apparent
 concentration read from the calibration curve
 and the true concentration assigned to the
 tow-concentration calibration standard
 exceeds 5 percent of the true concentration.
 the manufacturer shall determine the source
 of error and correct it then repeat the three-
 point calibration.
   5-2.3.2  Verification of Manufacturer's
 Calibration Standards. Before using a
 standard, the manufacturer shall verify each
 calibration standard (a) by comparing it to
 gas mixtures prepared (with 99 mole percent
 vinyl chloride) in accordance with the
 procedure described in Section 7.1 or (b)
 calibrating it against vinyl chloride cylinder
 Standard Reference Materials (SUM'S)
 prepared by the National Bureau of
 Standards, if such SUM'S are available. The
 agreement between the initially determined
 concentration value and the verification
 concentration value must be within  ±5
 percent. The manufacturer must reverify all
 calibration standards on a time interval
 consistent with the shelf life of the cylinder
 standards sold.
   5J.4  Audit Cylinder Standards (2). Gas
 mixture standards with concentrations
 known only to the person supervising the
 analysis of samples. The audit cylinder
 standards shall be identically prepared as
 those in Section 523 (vinyl chloride in
 nitrogen cylinders). The concentrations of the
 audit cylinder should be: one low-
 concentration cylinder in the range of 5 to 20
 ppm vinyl chloride and one high-
 concentration cylinder in the range of 20 to 50
 ppm. When available, the tester may obtain
 audit cylinders by contacting: Environmental
 Protection Agency, Environmental Monitoring
 Systems Laboratory. Quality Assurance
 Division (MO-77). Research Triangle Park.
 North Carolina 27711. Audit cylinders
 obtained from a commercial gas
 manufacturer may be used provided: (a) the
 gas manufacturer certifies the audit cylinder
 as described in Section 5^3.1. and (b) the gas
 manufacturer obtains an independent
 analysis of the audit cylinders to verify this
 analysis. Independent analysis is defined
hen to mean analysis performed by an
individual different than the individual who
performs the gaa manufacturer's analysis,
while using calibration standards and
analysis equipment different from those used
for the gas manufacturer's analysis.
Verification is complete and acceptable when
the independent analysis concentration is
within ±S percent of the gas manufacturer's
concentration.

6.Proc*dun
  &1  Sampling. Assemble the sample brain
as shown hi Figure 105-1. A bag leak check
should have been performed previously
 according to Section 732. Join the quick
connects as illustrated, and determine that all
 connection between the bag and the probe
are tight Place the end of the probe at the
 centroid of the stack and start the pump with
 the needle valve adjusted to yield a flow that
 will 811 over 50 percent of bag volume hi the
specific sample period. After allowing
sufficient time to purge the line several times,
change the vacuum line from the container to
 the bag and evacuate the bag until the
 rotameter indicates no flow. Then reposition
 the sample and vacuum lines and begin the
 actual sampling, keeping the rate
proportional to the stack velocity. At all
 times, 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. Protect the bag container from
 sunlight.
   6.2  Sample storage. Keep the sample bags
 out of direct sunlight. When at all possible.
 analysis is to be performed within 24 hours.
 but in no case in excess of 72 hours of sample
 collection. Aluminized Mylar bag samples
 must be analyzed within 24 hours.
   8.3  Sample Recovery. With a new piece of
 Teflon tubing identified for that bag. connect
 a bag inlet valve to the gas chromatograph
 sample valve. Switch the valve to receive gas
 from the bag through the sample loop.
 Arrange the equipment so the sample gas
 passes from the sample valve to 100-ml/mhv
 rotameter with flow control valve followd by
 a charcoal tube and a 1-in. H,O pressure
 gauge. The tester may maintain the sample
 flow either by a vacuum pump or container
 pressurization if the collection bag remains in
 the rigid container. After sample loop purging
 is ceased, allow the pressure gauge to return
 to zero before activating the gas sampling--
 valve.
   6.4  Analysis. Set the column temperature
 to 100* C and the detector temperature to 150*
 C. When optimum hydrogen and oxygen flow
 rates have been determined, verify and
 maintain these flow rates during all
 chromatography operations. Using zero
 helium or nitrogen as the carrier gas,
 establish a flow rate in the range consistent
 with the manufacturer's requirements for
 satisfactory detector operation. A Sow rate of
 approximately 40 ml/min should produce
 adequate separations. Observe the base line
 periodically and determine that the noise
 level has stabilized and that base line drift
 has ceased. Purge the sample loop for 30
 seconds at the rate of 100 ml/min. shut off
 flow, allow the sample loop pressure to reach
 atmospheric pressure as indicated by the HtO
 manometer, then activate the sample valve.
 Record the injection time (the position of the
 pen on the chart at the time of sample
 injection), sample number,  sample loop
 temperature, column temperature, carrier gas
 flow rate, chart speed, and attenuator setting.
 Record the barometeric pressure. From the
 chart note the peak having the retention time
 corresponding to vinyl chloride as.
 determined in Section 7.2.1. Measure the
 vinyl chloride peak area. Am, by use of a disc
 integrator, electronic integrator, or a
 planimeter. Measure and record the peak
 heights, HV Record A. and retention time.
 Repeat the injection at least two times or
 until two consecutive values for the total area
 of the vinyl chloride peak do not vary more
 than 5 percent Use the average value for
 these two total areas to compute the bag
, concentration.
   Compare the ratio of H. to A. for the vinyl
 chloride sample with the same ratio for the
 standard peak that is closest in height If
 these ratios differ by more than 10 percent
 the vinyl chloride peak may not be pure
 (possibly acetaldehyde is present) and the
 secondary column should be employed (see
 Section 4.3JL2).
   &5 Determination of Bag Water Vapor
 Content Measure the ambient temperature
                                                             IOC-19

-------
         Federal Register / Vol. 47, No. 173 / Tuesday, September 7,1982 / Rules and Regulations
FILTER (GLASS WOOL)
/


agfgT[
   TEFLON
/SAMPLE LINE
VACUUM LINE
    STACK WAUL
                                 QUICK
                               CONNECTS
                                 (MALE),
                      BALL
                     CHECKS
     FLOW METER
                                CONNECTS U
                                (FEMALE)
                           TEOLAft OR
                           AIUUIN1ZEO
                           MYLAR BAG
                             RIGID LEAK-PROOF
                                CONTAINER
                                CHARCOALTUBE
                                                    PUMP
     Figure 106-1. Iniegrated-bag sampling train, {Mention of trade names
     or specific products does not constitute endorsement by the Environ-
     mental Protection Agency.)
                                      106-20

-------
           Federal Register /  Vol. 47,  No.  173  /  Tuesday. September 7. 1982 /  Rules  and Regulations
and barometric pressure near the bag. From a
water saturation vapor pressure table,
determine and record the water vapor
content of the bag as a decimal figure.
(Assume the relative humidity to be 100
percent unless a lesser value is known.]

7. Preparation of Standard Gas Mixtures,
Calibration, and Quality Assurance
  7.1  Preparation of Vinyl Chloride
Standard Gas Mixtures. (Optional
Procedure—delete if cylinder standards are
used.) Evacuate a 16-inch square Tedlar bag
that has passed a leak check (described in
Section 733) and meter in 5.0 liters of
nitrogen. While the bag ia filling, use the 0.5-
ml syringe to inject 250 pi of 99.9-f percent
vinyl chloride gaa through the wall of the bag.
Upon withdrawing the syringe, immediately
cover the resulting hole with a piece of
adhesive tape. The bag now contains a vinyl
chloride concentration of SO ppm. In a like
manner use the 50 ui syringe to prepare gas
mixtures having 10- and 5-ppm vinyl chloride
concentrations. Place each bag on a smooth
surface and alternately depress opposite
sides of the bag SO times to further mix the
eases. These gas mixture standards may be
used for 10 days from the date of preparation.
after which time new gas mixtures most be
prepared. (Caution: Contamination may be a
problem when a bag is reused if the new gas
mixture standard is a lower concentration
than the previous gas mixture standard.)
  73.  Calibration.
  7.2.1  Determination of Vinyl Chloride
Retention Time. (This section can be
performed simultaneously with Section 7^2.)
Establish chromatograph conditions identical
with those in Section 8.4 above. Determine
proper attenuator position. Flush the
timpK"g loop with zero helium or nitrogen
and activate the sample valve. Record the
injection time, sample loop temperature,
column temperature, carrier gas flow rate,
chart speed, and attenuator setting. Record
peaks and detector responses that occur in
the absence of vinyl chloride. Maintain
conditions with the equipment plumbing
arranged identically to Section 6.3, and flush
the sample loop for 30 seconds at the rate of
100 ml/min with one of the vinyl chloride
calibration mixtures. Then activate the
sample valve. Record the injection time.
Select the peak that corresponds to vinyl
chloride. Measure the distance on the chart
from the injection time to the time at which
the peak maximum occurs. This quantity
divided by the chart speed is defined as the
retention time. Since other organics may be
present in the sample, positive identification
of the vinyl chloride peak must be made.
  7.Z2  Preparation of Chromatograph
Calibration Curve. Make a GC measurement
of each gas mixture standard (described in
Section 5.2.3 or 7.1) using conditions identical
with those listed in Sections 6.3 and 6.4. Flush
the sampling loop for 30 seconds at the rate
of 100 ml/min with one of the standard
mixtures, and activate the sample valve.
Record the concentration of vinyl chloride
injected (CJ, attenuator setting, chart speed.
peak area, sample loop temperature, column
temperature, carrier gas flow rate, and
retention time. Record the barometric
pressure. Calculate A«, the peak area
multiplied by the attenuator setting. Repeat
until two consecutive injection areas are
within 5 percent, then plot the average of
those two value* versus Q. When the other
standard gas mixtures have been similarly
analyzed and plotted, draw a straight line
through the points derived by the least
squares method. Perform calibration daily, or
before and after the analysis of each
emission test set of bag samples, whichever
is more frequent For each group of sample
analyses, use the average of the two
calibration curves which bracket that group
to determine the respective sample
concentrations.  If the two calibration curves
differ by more than 5 percent from their mean
value, then report the final results by both
calibration curves.
  73  Quality Assurance.
  7.3.1  Analysis Audit Immediately after
the preparation  of the calibration curve and
prior to the sample analyses, perform the
analysis audit described in Appendix C  .
Procedure 2: "Procedure for Field Auditing
GC Analysis."
  7.3.2  Bag Leak Checks. Checking of bags
for leaks is required  after bag use and
strongly recommended before bag use. After
each use, connect a water manometer and
pressurize the bag to 5 to 10 cm HiO (2 to 4
in. H»O). Allow  to stand for 10 min. Any
displacement in the water manometer
indicates a leak. Also, check the rigid
container for leaks in this manner. (Note:  An
alternative leak check method is to pressurize
the bag to 5 to 10 cm HiO and allow it to
stand overnight A deflated bag indicates a
leak.) For each sample bag in its rigid
container, place a rotameter in line between
the bag and the pump inlet Evacuate the  bag.
Failure of the rotameter to register zero flow
when the bag appears to be empty indicates a
leak.
  8, Calculations.
  &1  Determine the sample peak area, Ac,
as follows:
  8.2  Vinyl Chloride Concentrations. From
the calibration curves described in Section
7.2.2. determine the average concentration
value of vinyl chloride, C,, that corresponds
to Ac. the sample peak area. Calculate the
concentration of vinyl chloride in the bag. C>
as follows:
                             Eq.  106-2
                              Eq.  106-1
Where:
  A.=Measured peak area.
  At** Attenuation factor.
Where:
  Pr™ Reference pressure, the laboratory
    pressure recorded during calibration, mm
    Hg.

  TI« Sample loop temperature on the
    absolute scale at the time of analysis. "K.

  ^Laboratory pressure at time of analysis,
    mm Hg.

  T,=Reference temperature, the sample
    loop temperature recorded during
    calibration, "K.

  B»»=Water vapor content of the bag
    sample, as analyzed.
  9. Bibliography.

  •L Brown D.W.. E.W. Loy, and MIL
Stephenson, Vinyl Chloride Monitoring Near
the B. F. Goodrich Chemical Company in
Louisville, KY. Region IV. U.S. Environmental
Protection Agency, Surveillance and Analysis
Division. Athens,  GA. June 24.1974.
  2. G.D. Clayton  and Associates. Evaluation
of a Collection and Analytical Procedure for
Vinyl Chloride in Air. U.S. Environmental
Protection Agency, Research Triangle Park.
• N.C EPA Contract No. 68-02-1401 Task
Order No. 2. EPA  Report No. 75-VCL-l.
December 13,1974.
  3. Midwest Research Institute.
Standardization of Stationary Source
Emission Method  for Vinyl Chloride. U.S.
Environmental Protection Agency. Research
Triangle Park. N.C Publication No. EPA-COO/
4-77-026. May 1S77.
  4. Scheil, G. and M.C Sharp. Collaborative
Testing of EPA Method 106 (Vinyl Chloride)
that Will Provide  for a Standardized
Stationary Source Emission Measurement
Method. U.S. Environmental Protection
Agency. Research Triangle Park, N.C
Publication No. EPA 600/4-78-05& October
1978.  .
                                                         106-21

-------
40 CFR Part 61, Appendix B
Final, promulgated
            METHOD  107—DETERMINATION  OF  VINYL  CHLORIDE  CONTENT OF  INPROCESS
         WASTEWATER  SAMPLES,  AND  VINYL CHLORIDE  CONTENT OF  POLYVINYL  CHLORIDE
                     RESIN,  SLURRY,  WET CAKE, AND LATEX  SAMPLES
          Introduction
               Performance of this  method  should  not be attempted  by  persons
          unfamiliar with the operation of a gas  chromatograph (GC),  nor  by
          those who  are unfamiliar  with source sampling, because knowledge
          beyond the scope of this  presentation is required.   Care must be
          exercised  to  prevent exposure of sampling personnel  to vinyl  chloride,
          a carcinogen.
          1.  Applicability and Principle
               1.1   Applicability.   This method applies to the measurement of
          the vinyl  chloride monomer (VCM) content of inprocess wastewater
          samples,  and  the residual vinyl  chloride monomer (RVCM)  content of
          polyvinyl  chloride (PVC)  resins, wet cake, slurry,  and latex samples.
          It cannot be  used for polymer in fused forms, such as sheet or  cubes.
          This method is not acceptable where methods from Section 304(h) of
          the Clean Water Act, 33 U.S.C. 1251 et seq. (the Federal Water
          Pollution Control Amendments of 1972 as amended by the Clean Water
          Act of 1977)  are required.
                1.2  Principle.  The basis for this method relates to the vapor
          equilibrium  that is  established between RVCM, PVC resin, water, and
          air  in a closed  system.  The  RVCM  in a  PVC resin will equilibrate
          rapidly in a closed  vessel,  provided that  the temperature of the PVC
          resin is maintained  above the glass  transition  temperature of  that
           specific  resin.
                                        107-1

-------
2.  Range and Sensitivity
     The lower limit of detection of vinyl chloride will vary
according to the chromatograph used.  Values reported include
1 x 10   mg and 4 x 10"  mg.   With proper calibration, the upper
limit may be extended as needed.
3.  Interferences
     The chromatograph columns and the corresponding operating
parameters herein described normally provide an adequate resolution
of vinyl chloride; however, resolution interferences may be
encountered on some sources.   Therefore, the chromatograph operator
shall select the column and operating parameters best suited to his
particular analysis requirements* subject to the approval of the
Administrator.  Approval is automatic provided that the tester
produces confirming data through an adequate supplemental analytical
technique, such as analysis with a different column or GC/mass
spectroscopy, and has the data available for review by the
Administrator.
4.  Precision and Reproducibility
     An inter!aboratory comparison between seven laboratories of
three resin samples, each split into three parts, yielded a standard
deviation of 2.63 percent for a sample with a mean of 2.09 ppm,
4.16 percent for a sample with a mean of 1.66 ppm, and 5.29 percent
for a sample with a mean of 62.66 ppm.
5.  Safety
     Do not release vinyl chloride to the laboratory atmosphere
 during  preparation of standards.  Venting or purging with VCM/air
                               107-2

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mixtures must be held to a minimum.  When they are required,  the vapor
must be routed to outside air.  Vinyl chloride, even at low ppm
levels, must never be vented inside the laboratory.  After vials have
been analyzed, the gas must be vented prior to removal  of the vial
from the instrument turntable.  Vials must be vented through  a
hypodermic needle connected to an activated charcoal tube to
prevent release of vinyl chloride into the laboratory atmosphere.
The charcoal must be replaced prior to vinyl chloride breakthrough.
6.  Apparatus
     6.1  Sampling.  The following equipment is required:
     6.1.1  Glass Bottles.  60-ml (2-oz) capacity, with wax-lined
screw-on tops, for PVC samples.
     6.T.2  Glass Vials.  50-ml capacity Hypo-vial, sealed with Teflon
faced Ti!f-Bond discr, for water samples.
     6.1.3  Adhesive Tape.  To prevent loosening of bottle tops.
     6.2  Sample Recovery.  The following equipment is required:
     6.2.1  Glass Vials.  With butyl rubber septa, Perkin-Elmer
Corporation Nos. 0105-0129 (glass vials), BOO!-0728 (gray butyl rubber
septum, plug style), 0105-0131 (butyl rubber septa), or equivalents.
The seals must be made from butyl rubber.  Silicone rubber seals are
not acceptable.
     6.2.2  Analytical Balance.  Capable of weighing to +0.0001 gram.
     6.2.3  Vial Sealer.  Perkin-Elmer No. 105-0106, or equivalent.
     6.2.4  Syringe.  100-pl capacity, precision  series "A"
No. 010025, or equivalent.
     6.3  Analysis.   The  following  equipment  is required:
                                    107-3

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     6.3.1  Gas Chromatograph.  Perkin-Elmer Corporation Model F-40,
F-42, or F-45 Head-Space Analyzer, or equivalent.  Equipped with
backflush accessory.
     6.3.2  Chromatographic Columns.  Stainless steel 1 m by 3.2 mm
and 2 m by 3.2 mm, both containing 50/80-mesh Porapak Q.  The analyst
may use other columns provided that the precision and accuracy of the
analysis of vinyl chloride standards ar?   t impaired and he has
available for review information confirming that there is adequate
resolution of the vinyl chloride peak.  (Adeouate resolution is
defined as an area overlap of not more than iO percent of the vinyl
chloride peak by an interferent peak.  Calculation of area overlap is
explained in Appendix C, Procedure 1:  "Determination of Adequate
Chromatographic Peak Resolution.")  Two 1.83 m columns, each containing
1 percent Carbowax 1500 on Carbopak B, have been suggested for samples
containing acetaldehyde.
     6.3.3  Thermometer.  0 to 100° C, accurate to +0.1° C, Perkin-Elmer
No. 105-0109, or equivalent.
     6.3.4  Sample Tray Thermostat System.  Perkin-Elmer No.  105-0103,
or equivalent.
     6.3.5  Septa.  Sandwich type, for automatic dosing, 13 mm,
Perkin-Elmer No. 105-1008, or equivalent.
     6.3.6  Integrator-Recorder.  Hewlett-Packard Model 3380A, or
equivalent.
     6.3.7  Filter Drier Assembly (3).  Perkin-Elmer No.  2230117,
or equivalent.
                               107-4

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     6.3.8  Soap Film Flowmeter.  Hewlett Packard No. 0101-0113,
or equivalent.
     6.3.9  Regulators.  For required gas cylinders.
     6.3.10  Headspace Vial Pre-Pressurizer.  Nitrogen pressurized
hypodermic needle inside protective shield.  (Blueprint available
from Test Support Section, Emission Measurement Branch, Office of
Air Quality Planning and Standards, Environmental Protection Agency,
Mail Drop 19, Research Triangle Park, N.C. 27711.)
7.  Reagents
     Use only reagents that are of chromatographic grade.
     7.1  Analysis.   The following items are required for analysis:
     7.1.1  Hydrogen.  Zero grade.
     7.1.2  Nitrogen.  Zero grade.
     7.1.3  Air.  Zero grade.
     7.2  Calibration.  The following items are required for calibration:
     7.2.1  Cylinder Standards (4).  Gas mixture standards (50-, 500-,
2000- and 4000-ppm vinyl chloride in nitrogen cylinders).  The
tester may use cylinder standards to directly prepare a chromatograph
calibration curve as described in Section 9.2, if the following
conditions are met:   (a)  The manufacturer certifies the gas
composition with an accuracy of +3 percent or better (see
Section 7.2.1.1).  (b)  The manufacturer recommends a maximum shelf
life over which the gas concentration does not change by greater
than +5 percent from the certified value,   (c)  The manufacturer
affixes the date of gas cylinder  preparation, certified vinyl
                                107-5

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chloride concentration, and recommended maximum shelf life to the
cylinder before shipment to the buyer.
     7.2.1.1  Cylinder Standards Certification.  The manufacturer
shall certify the concentration of vinyl chloride in nitrogen in
each cylinder by (a) directly analyzing each cylinder and (b)
calibrating his analytical procedure on the day of cylinder analysis.
To calibrate his analytical procedure, the manufacturer shall use,
as a minimum, a 3-point calibration curve.  It is recommended
that the manufacturer maintain (1) a high-concentration calibration
standard (between 4000 and 8000 ppm) to prepare his calibration curve
by an appropriate dilution technique and (2) a low-concentration
calibration standard (between 50 and 500 ppm) to verify the dilution
technique used.  If the difference between the apparent concentration
read from the calibration curve and the true concentration assigned
to the low-concentration calibration standard exceeds 5 percent of
the true concentration, the manufacturer shall determine the source
of error and correct it, then repeat the 3-point calibration.
     7.2.1.2  Verification of Manufacturer's Calibration Standards.
Before using, the manufacturer shall verify each calibration
standard by (a) comparing it to gas mixtures prepared (with 99 mole
percent vinyl chloride) in accordance with the procedure described
in Section 7.1 of Method 106 or by (b) calibrating it against vinyl
chloride cylinder Standard Reference Materials (SRM's) prepared by
the National Bureau of Standards, if such SRM's are available.  The
agreement between the initially determined concentration value and the
                               107-6

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 verification  concentration  value must  be within  +5  percent.  The
 manufacturer  must  reverify  all calibration  standards on a time
 interval  consistent with  the  shelf  life of  the cylinder standards
 sold.
 8.   Procedure
     8.1  Sampling.
     8.1.1  PVC  Sampling.   Allow the resin  or slurry to flow from
 a tap on  the  tank  or silo until the tap line has been well purged.
 Extend and fill  a  60-ml sample bottle under the  tap, and immediately
 tighten a cap on the bottle.  Wrap adhesive tape around the cap
 and  bottle to prevent the cap from loosening.  Place an identifying
 label on each bottle, and record the date, time, and sample
 location both on the bottles and in a log book.
     8.1.2  Water Sampling.   Prior to use, the 50-ml vials (without the
discs) must be capped with aluminum foil  and heated in a muffle furnace
at 400° C for at least 1 hour to destroy or remove any organic
matter that could interfere  with analysis.   At the sampling location
fill the vials bubble-free to overflowing so that a convex meniscus
forms at the top.  The excess water is displaced as the sealing disc
is carefully placed, with the Teflon side down,  on the opening  of the
vial.
     Place the aluminum seal over the disc and the neck of the  vial,
and crimp into place.   Affix an identifying label on the bottle, and
record the date, time, and sample location both  on the vials  and in a
log book.  All samples must  be kept refrigerated until  analyzed.
                               107-7

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     8.2  Sample Recovery.  Samples must be run within 24 hours.
     8.2.1  Resin Samples.  The weight of the resin used must be
between 3.5 and 4.5 grams.  An exact weight must be obtained
(+0.0001 g) for each sample.  In the case of suspension resins,
a volumetric cup can be prepared for holding the required
amount of sample.  When the cup is used, open the sample bottle,
and add the cup volume of resin to the tared sample vial (tared,
including septum and aluminum cap).  Obtain the exact sample weight,
add 100 ul or about two equal drops of distilled water, and immediately
seal the vial.  Report this value on the data sheet; it is required
for calculation of RVCM.  In the case of dispersion resins, the
cup cannot be used.  Weigh the sample in an aluminum dish, transfer
the sample to the tared vial, and accurately weigh it in the vial.
After prepressurization of the samples, condition them for a minimum
of 1 hour in the 90° C bath.  Do not exceed 5 hours.
     Note:  Some aluminum vial caps have a center section that must
be removed prior to placing into sample tray.   If the cap is not
removed, the injection needle, will be damaged.
     8.2.2  Suspension Resin Slurry and Wet Cake Samples.   Decant
the water from a wet cake sample, and turn the sample bottle upside
down onto a paper towel.  Wait for the water to drain, place
                               107-R

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approximately 0.2 to 4.0 grams of the wet cake sample in a
tared vial (tared, including septum and aluminum cap) and
seal immediately.  Then determine the sample weight (+0.0001 g).
All samples must be prepressurized and then conditioned for
1 hour at 90° C.  A sample of wet cake is used to determine total
solids (TS).  This is required for calculating the RVCM.
     8.2.3  Dispersion Resin Slurry and Geon Latex Samples.  The
materials should not be filtered.  Sample must be thoroughly mixed.
Using a tared vial (tared, including septum and aluminum cap) add
approximately eight drops (0.25 to 0.35 g) of slurry or latex using
a medicine dropper.  This should be done immediately after mixing.
Seal the vial as soon as possible.  Determine sample weight
(+0.0001 g).  After prepressurization, condition the vial for
1 hour at 90° C in the analyzer bath.  Determine the TS on the
slurry sample (Section 8.3.5).
     8.2.4  Inprocess Wastewater Samples.  Using a tared vial
(tared, including septum and aluminum cap) quickly add approximately
1 cc of water using a medicine dropper.  Seal the vial as soon  as
possible.  Determine sample weight (+0.0001 g).  Prepressurize
the vial, and then condition for  1 to 2 hours as required at 90°  C
in the analyzer bath.
     8.3  Analysis
     8.3.1  Preparation of Equipment.   Install the chromatographic
column and  condition overnight at 160°  C.   In the  first operation,
Porapak columns must be purged for 1  hour at 230°  C.
                                 107-9

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Do not connect the exit end of the column to the detector while
conditioning.  Hydrogen and air to the detector must be turned
off while the column is disconnected.
     8.3.1.1   Flow Rate Adjustments.  Adjust flow rates as follows:
     a.   Nitrogen Carrier Gas.  Set regulator on cylinder to
read 50 psig.  Set regulator on chromatograph to produce a flow
rate of 30.0 cc/min.  Accurately measure the flow rate at the
exit end of the column using the soap film flowmeter and a stop-
watch, with the oven and column at the analysis temperature.
After the instrument program advances to the "B" (backflush) mode,
adjust the nitrogen pressure regulator to exactly balance the
nitrogen flow rate at the detector as was obtained in the "A" mode.
     b.  Vial  Prepressurizer Nitrogen.  After the nitrogen carrier
is set, solve the following equation and adjust the pressure on the
vial prepressurizer accordingly.
                               Pwl ' Pw2
Pl      7T5T
                                           - 10 k Pa
Where:
     T,    s Ambient temperature, °K.
     Jy    s Conditioning bath temperature, °K.
     P,    * Gas chromatograph absolute dosing pressure (analysis
             mode), k Pa.
     Pwl   = Water vapor pressure @ 90° C  (525.8 mm Hg).
     Pw2   = Water vaP°r pressure @ 22° C  (19.8 mm Hg).
     7.50  = mm Hg per k Pa.
                               107-10

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     10 k Pa  = Factor to adjust the prepressurized pressure to
                slightly less than the dosing pressure.
     Because of gauge errors, the apparatus may over-pressurize the
vial.  If the vial pressure is at or higher than the dosing pressure,
an audible double injection will occur.  If the vial pressure is too
low, errors will occur on resin samples because of inadequate time for
head-space gas equilibrium.  This condition can be avoided by running
several standard gas samples at various pressures around the
calculated pressure, and then selecting the highest pressure that does
not produce a double injection.  All samples and standards must be
pressurized for 60 seconds using the vial prepressurizer.  The vial
is then placed into the 90C C conditioning bath and tested for leakage
by placing a drop of water on the septum at the needle hole.  A clean,
burr-free needle is mandatory.
     c.  Burner Air Supply.  Set regulator on cylinder to read 50 psig.
Set regulator on chromatograph to supply air to burner at a rate
between 250 and 300 cc/min.  Check with bubble flowmeter.
     d.  Hydrogen Supply.  Set regulator on cylinder to read 30 psig.
Set regulator on chromatograph to supply approximately 35+5 cc/min.
Optimize hydrogen flow to yield the most sensitive detector response
without extinguishing the flame.  Check flow with bubble meter and
record this flow.
     8.3.1.2  Temperature Adjustments.  Set temperatures as follows:
     a.  Oven (chromatograph column),  140° C.
     b.  Dosing Line, 150° C.
     c.  Injection Block, 170° C.
     d.  Sample Chamber, Water Temperature, 90° C i 1.0° C.

-------
     8.3.1.3  Ignition of Flame lonization Detector.   Ignite  the
detector according to the manufacturer's  instructions.
     8.3.1.4  Amplifier Balance.  Balance the  amplifier  according
to the manufacturer's instructions.
     8.3.2  Programming the Chromatograph.   Program the  chromatograph
as follows:
     a.  I-Oosing or Injection Time.  The normal  setting is 2 seconds.
     b.  A-11 Analysis Time."  The normal setting  is approximately
70 percent of the VCM retention time.  When  this  timer
terminates, the programmer Initiates backflushing of the first column.
     c.  B-Backflushing Time.   The normal setting is double the
"analysis tirae."
     d.  H-Stabllizatlon Time.  The normal setting is 0.5 min to
1.0 min.
     e.  X-Numfaer of Analyses Per Sample.   The normal  setting is one.
     8.3.3  Preparation of Sample Turntable.   Before placing any
sample into turntable,  be certain that the center section of the
aluminum cap has been removed.  All  samples and standards must be
pressurized for 60 seconds by using the vial  prepressurizer.   The
numbered sample vials should be placed in  the corresponding numbered
positions in the turntable.   Insert samples  in the following order:
     Positions 1 and 2—Old 2000-ppm standards for conditioning.   These
are necessary only after the analyzer has  not been used for 24 hours or
longer.
     Position 3 — 50-ppm standard,  freshly prepared.
     Position 4 — 500-ppm standard,  freshly  prepared.
                                107-12

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     Position 5 — 2000-ppm standard, freshly prepared.
     Position 6 — 4000-ppm standard, freshly prepared.
     Position 7 — Sample No. 7 (This is the first sample of the day,
but is given as 7 to be consistent with the turntable and the
integrator printout.)
     After all samples have been positioned, insert the second set of
50-, 500-, 2000-, and 4000-ppm standards.  Samples, including
standards, must be conditioned in the bath of 90° C for 1 hour (not
to exceed 5 hours).
     8.3.4  Start Chromatograph Program.  When all samples, including
standards, have been conditioned at  90° C for 1 hour, start the
analysis program according to the manufacturer's instructions.  These
instructions must be carefully followed when starting and stopping a
program to prevent damage to the dosing assembly.
     8.3.5  Determination of TS.  For wet cake, slurry,
resin solution, and PVC latex samples, determine TS for each sample
by accurately weighing approximately 3 to 4 grams of sample in an
aluminum pan before and after placing in a draft oven (105 to 110° C).
Samples must be dried to constant weight.  After first weighing, return
the pan to the oven for a short period of time, and then reweigh to
verify complete dryness.  The TS are then calculated as the final
sample weight divided by initial sample weight.
9.  Calibration
     Calibration  is  to be performed  each 8-hour period when the instru-
ment is used.  Each  day, prior  to running samples, the column should
be conditioned by running two 2000-ppm standards from the previous day.
                                107-13

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     9.1   Preparation of Standards.  Calibration standards are  prepared
as follows:   Place 100 ul or about two equal drops of distilled water
in the sample vial, then fill the vial with the VCM/nitrogen
standard, rapidly seat the septum, and seal with the aluminum cap.   Use
a 1/8-in. stainless steel line from the cylinder to the vial.   Do  not
use rubber or tygon tubing.  The sample line from the cylinder  must
be purged (into a properly vented hood) for several minutes prior  to
fill the  vials.  After purging, reduce the flow rate to
500 to 1000 cc/min.  Place end of tubing into vial (near bottom).
Position  a septum on top of the vial, pressing it against the 1/8-in.
filling tub* to minimize the size of the vent opening.  This is
necessary to minimize mixing air with the standard in the vial.  Each
vial is to be purged with standard for 90 seconds, during which time
the filling tube 1s gradually slid to the top of the vial.  After  the
90 seconds, the tube 1s removed with the septum, simultaneously
sealing the vial.  Practice will be necessary to develop good technique.
Rubber gloves should be worn during the above operations.  The  sealed
vial must then be pressurized for 60 seconds using the vial
prepressurizer.  Test the vial for leakage by placing a drop of water
on the septum at the needle hole.
     9.2   Preparation of Chromatograph Calibration Curve.
     Prepare two 50-, 500-, 2000-, and 4000-ppm standard samples.  Run
the calibration samples in exactly the same manner as regular samples.
Plot AS>  the integrator area counts for each standard sample, versus
C^j the  concentration of vinyl chloride in each standard sample.   Draw
a straight  line through the points derived by the least squares method.
                               107-14

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10.  Calculations
     10.1  Response Factor.  If the calibration curve described in
Section 9.2 passes through zero, a response factor, Rf, may be used to
compute vinyl chloride concentrations.  To compute a response factor,
divide any particular A  by the corresponding C .
                       s                       c

                                  Rf * -f-                   Eq. 107-1
                                        c
If the calibration curve does not pass through zero, the calibration curve
must be employed to calculate each sample concentration unless the error
introduced by using a particular R- is known.
     10.2  Residual Vinyl Chloride Monomer Concentration, (Crvc) or
Vinyl Chloride Monomer Concentration.  Calculate Cryc in ppm or mg/kg
as follows:
     c
            **"*
      rvc
M.. V
                 T2 + *w " ' T5> T2
Eq.  107-2
Where:
     A   * Chromatograph area counts of vinyl chloride for the sample.
     Pa  • Ambient atmospheric pressure, mm Hg.
      a
     Rf  * Response factor in area counts per ppm VCM.
     T,  » Ambient laboratory temperature, °K.
     My  * Molecular weight of VCM, 62.5 g/mole.
     V   * Volume of the vapor phase, cm .
     R   » Gas constant, (62360 on3)  (mm Hg/mole)  (°K).
     m   = Sample weight, g.
                                107-15

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    a —:
rvc  R.
                   K   « Henry's Law Constant for VCM in PVC § 90° C,
                         6.52 x 10"6 g/g/mm Hg.
                   TS  = Total  solids expressed as a decimal fraction.
                   Tg  = Equilibrium temperature, °K.
                   K^  « Henry's Law Constant for VCM in water § 90° C,
                         7 x 10   g/g/mm Hg.
                   Assuming the following conditions are met, these values can be
              substituted into Equation 107-2:
                   Pa = 750 mm Hg.
                    a
                                                                             •5
                   V  = Vial volume - sample volume (Fisher vials are 22.0 cm  and
                        Perkin-Elmer vials are 21.8 on ).
                   T] = 23° C or 296° K.
                   L, « 90° C or 363° K.
i.25 x  10"6(TS)(363) +  7.0  x  10"7  (1-TS)(363)
                   Results  calculated  using  these  equations  represent  concentration
              based on  the  total  sample.  To obtain  results  based  on dry  PVC  content,
              divide by T3.
              11.   References
                   1.   B.F. Goodrich.   Residual  Vinyl  Chloride Monomer Content of
              Polyvinyl Chloride  Resins,  Latex,  Wet  Cake,  Slurry and Water Samples.
              B.F.  Goodrich Chemical Group Standard  Test Procedure No.  1005-E.
              B.F.  Goodrich Technical  Center, Avon Lake, Ohio.  October 8, 1979.
750
196
65.5 (21.8 -
m(TS) m(l-TSV
1.36 0.9653,
62360 m
                                            107-16

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     2.  Berens, A.R.   The Diffusion of Vinyl Chloride in Polyvinyl
Chloride.  ACS—Division of Polymer Chemistry, Polymer Preprints ]_5^
(2):197.  1974.
     3.  Berens, A.R.   The Diffusion of Vinyl Chloride in Polyvinyl
Chloride.  ACS--Division of Polymer Chemistry, Polymer Preprints 1_5_
(2):203.  1974.
     4.  Berens, A.R., L.B. Crider, C.J. Tomanek, and J.M. Whitney.
Analysis for Vinyl Chloride in PVC Powders by Head—Space Gas
Chromatography.  Journal of Applied Polymer Science.  19:3169-3172.
1975.
     5.  Mansfield, R.A.  The Evaluation of Henry's Law Constant
(Kp) and Water Enhancement in the Perkin-Elmer Multifract F-40 Gas
Chromatograph.  B.F. Goodrich.  Avon Lake, Ohio.  February 10, 1978.
                                107-17

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          Federal  Register / Vol. 47. No. 173 /  Tuesday. September 7. 1982 / Rules  and Regulations
Method 107—Determination of Vinyl Chloride
Content of InptocMi Wastewater Sample*,
and Vinyl Chloride Content of Polyvinyl
Chloride Resin, Starry. Wet Cake, «nd Latex
Introduction
  Performance of this method should not be
attempted by persons unfamiliar with the
operation of a gas chroraatograph (GC). nor
by those who are •unfamiliar with source
fynrli"g. because knowledge beyond the
scope of this presentation is required. Care
most be exercised to prevent exposure of
tfrnpUng peraonnel to vinyl chloride a
cercinQgen.
  I. Applicability and Principle.
  11 Applicability. This method applies to
the measurement of the vinyl chloride
aonomer (VCM) content of inprocess
wastewater samples, and the residual vinyl
chloride monomer (RVCM) content of
poryrinyi chloride (PVQ resins, wet cake.
story, and latex samples. It cannot be used
fOT polymer in fused forms, such as sheet or
cubes. T*is method is not acceptable where
methods from Section 304(h) of the Clean
Water Act  33 U.S.C. 1251 el seq. (the Federal
Water Pollution Control Amendments of 1972
as smenbed by the Clean Water Act of 1977)
are required.
  12 Principle. The bans for this method
relates to the vapor equilibrium that is
established between RVCM. PVC resin.
water, and air in a dosed system. The RVCM
in a PVC resin will equilibrate rapidly in a
closed vessel provided that the temperature
of the PVC resin is maintained  above the
glass transition temperature of that specific
   2. Range and Sensitiviry. The lower limit of
 detection of vinyl chloride will vary
 according to the chromatograph used. Values
 reported include Ix 10-'mg and 4 x 10~7 mg.
 With proper calibration, the upper Umit may
 be extended as needed.
 M*Hi"f and Ihe correaponding operating
 umlmfnmtmfm t    .  j--.. rt^f! fMflniallv
 provide sn adequate resolution of vinyl
 chloride: however, resohition interferences
 may be encountered on some sources.
 Therefore, die chromatograph operator shall
 select the column and operating parameters
 best svnad to his particular analysis
 requirements, subject to the approval of the
 Administrator. Approval is automatic
 provided that the testa* produces confirming
 data through an adeqaate supplemental
 analytical technique, such as analysis with a
~ ai&erent column or GC/mesa spectiuscopy,
 and has me data available for review by the.
routed to outside air. Vinyl chloride, even at
low ppm levels, must never be vented inside
the laboratory. After vials have been
analyzed, the gas must be vented prior to
removal of the vial from the instrument
turntable. Vials must be vented through a
hypodermic needle connected to an activated
charcoal tube to prevent release of vinyl
chloride into the laboratory atmosphere. The
charcoal must be replaced prior to vinyl
chloride breakthrough.
   4. Precision and ftaprodudbiiity. An
 hrterleboratory comparison between seven
 laboratories of three resin samples, each split
 into three parts, yielded a standard deviation
 of 2J3 percent for a sample with a mean of
 240 ppm. 4.18 percent for a sample with a
 mean of 1M ppm. and 5J9 percent for a
 sample with a mean of 6246 ppm.
   & Safety. Do not release vmyl chloride to
 me laboratory atmosphere during preparation
 of standards. Venting or purging with VCM/
 air mixtures must be betd to a minimum.
 When they ens required, the vapor must  be
  0.1   Sampling. The following equipment is
required:
  6.1.1  Glass bottles. 60-ml (2-oz) capacity,
with wax-lined screw-on tops, for PVC
samples.
  8.13  Glass Vials. SO-ml capacity Hypo-
vial, sealed with Teflon faced Tuf-Bond discs.
for water samples.
  6.1 J  Adhesive Tape. To prevent
loosening of bottle tops.
  &2   Sample Recovery. The following
equipment is required:
  til  Glass Vials. With butyl rubber septa.
Perkin-Elmer Corporation Nos. 0105-0129
(glass vials), B001-0728 (gray butyl robber
septum, plug style). 0105-0131 (butyl rubber
septa), or equivalents. The seals must be
made from butyl robber. SUicone rubber seals
are not acceptable.
  &Z£  Analytical Balance. Capable of
weighing to ±00001 gram.
  6A3  Vial Sealer. Perldn-Elmer No. 105-
0106, or equivalent
  8-2.4  Syringe. 100-(U capacity, precision
series "A" No. 010025, or equivalent
  8J   Analysis. The following equipment is
required:
  6JJ.  Gas Chromatofraph. Parkin-Elmer
Corporation Model F-fO, F-42. or F-45 Head-
Space Analyser, or equivalent Equipped with
backfhish accessory.
  &&2 Chromatographic Columns. Stainless
steel 1 m by 3J mm and 2 m by 12 mm. both
containing 50/86-mesh Porapak Q. The
analyst may use other columns provided that
the precision and accuracy of the analysis of
vinyl chloride standards are not impaired and
he has available for review information
confirming that mere is adequate resolution
of the vinyl chloride peak. (Adequate
resohition is defined as an area overlap of
not more than 10 percent of the vinyl chloride
peak by an interferent peak. Calculation of
area overlap is explained in Appendix C.
Procedure 1: "Determination of Adequate
Chromatographic Peak Resolution.") Two
1.83 m columns, each containing 1 percent
Carbowax 1500 on Carbopak B. have been
suggested, for samples containing
acetaMehyde.
   6JJ Thermometer. 0 to 100* C. accurate
to ±0.1* C Perkin-Elmer No. 105-0108, or
equivalent
   (L3.4 Sample Tray Thermostat System.
Perkin-Elmer No. 105-0103. or equivalent
   8JJ Septa. Sandwich type, for automatic
 dosing. 13 mm. Perkin-Elmer No. 105-1008. or
 equivalent
   &3J Integrator-Recorder. Hewlett-
 Packard Modal 3380A. or equivalent
   8J.7 Filter Drier Assembly (3). Perkin-
 Elmer No. 2230117. or equivalent
   8A8  Soap Film  Flowmeter. Hewlett
 Packard No. 0101-0113. or equivalent
  6.3.9  Regulators. For required gas
cylinders.
  &3.10 Headspace Vial Pre-Pressurizer.
Nitrogen pressurized hypodermic needle
inside protective shield. (Blueprint available
from Test Support Section. Emission
Measurement Branch. Office of Air Quality
Planning and Standards. Environmental
Protection Agency.  Mail Drop 19, Research
Triangle Park. N.C  27711.)
  7. Reagents. Use only reagents that are of
Chromatographic grade.
  7.1 Analysis. The following items are
required for analysis:
  7.1.1  Hydrogen. Zero grade.
  7.12  'Nitrogen. Zero grade.
  7.L3  Air. Zero grade.
  72 Calibration. The following items are
required for calibration:   -
  7.2.1  Cylinder Standards (4). Gas mixture
standards (50-. 500-, 2000- and 4000-ppm vinyl
chloride in  nitrogen cylinders). The tester
may use cylinder standards to directly
prepare a chromatograph calibration curve as
described in Section 9.2. if the following
conditions  are met (a) The manufacturer
certifies the gas composition with an
accuracy of ±3 percent or better (see Section
7.2.1.1), (b)  The manufacturer recommends a
maxfrnim shelf life over which the gas
concentration does not change by greater
than ±S percent from the certified value, (c)
The manufacturer affixes the date of gas
cylinder preparation, certified vinyl chloride
concentration, and recommended maximum
shelf life to the cylinder before shipment to
the buyer.
  7.2.1.1 Cylinder Standards Certification.
The manufacturer shall certify the
concentration of vinyl chloride in nitrogen in
each cylinder by (a) directly analyzing each
cylinder and (b) calibrating his analytical
procedure on the day of cylinder analysis. To
calibrate his analytical procedure, the
manufacturer shall use. as a minimum, a 3-
point calibration curve. It is recommended
that the manufacturer maintain (1) a high-
concentration calibration standard (between  .
4000 and 8000 ppm) to prepare his calibration
curve by an appropriate dilution technique
and (2) a low-concentration calibration
standard (between 50 and 500 ppm) to verify
the dilution technique used. If the difference
between the apparent concentration read
from die calibration curve and the true
concentration assigned to the low-
concentration calibration standard exceeds 5
percent of  the true concentration, the
m«ftyf-f
-------
           Federal Register / Vol. 47, No.  173 /  Tuesday, September 7, 1982 /  Rules and Regulations
 percent The manufacturer must reverify ail
 calibration standards on a time interval
 consistent with the shelf life of the cylinder
 standard* sold.      -      - •
  ^Procedure.
  8.1  Sampling.          «
  8.1.1  PVC Sampling. Allow the resin or
 slurry to flow from a tap on the tank or silo
 until the tap line has been well purged.
 Extend and fill a 60-ml sample bottle under
 the tap. and immediately tighten a cap on the
 bottle. Wrap adhesive tape around the cap
 and bottle to prevent the cap from loosening.
 Place an identifying label on each bottle, and
 mcord the date, time, and sample  location
 both on the bottles and in a log book.
  8.12  Water Sampling. Prior to  use. the 50-
 ml vials (without the discs) most be capped
 with aluminum foil and heated in a muffle
 furnace at 400* C for at least 1 hour to destroy
 or remove any organic matter that could
 interfere with analysis. At the sampling
 location fill the vials bubble-free to
 overflowing so that a convex meniscus forms
 at the top. The excess water is displaced as
 the sealing disc is carefully placed, with the
.Teflon side down, on the opening of the vial
  Place the aluminum seal over the disc and
 the neck of the vial, and crimp into place.
 Affix an identifying label on the bottle, and
 record the date. time, and sample  location
 both on the vials and in a log book All
 samples must be kept refrigerated until
 analyzed.
  &2  Sample Recovery. Samples must be
 ran within 24 hoars.
  8JL1  Resin Samples. The weight of the
 resin used must be between 3JS and 4£
 grams. An exact weight must be obtained
 (±00001 g) for each sample. In the case of
 suspension resins, a volumetric cup can be "•
 prepared for holding the required amount of
 sample. When the cup is used, open the
 sample bottle, and add the cup volume of
 resin to the tared sample vial (tared.
 including septum and •fcmrfn*"* cap). Obtain
 the exact sample weight, add lOOpd or about
 two equal drops of distilled water, and
 immediately seal the viaL Report this value
 on the data sheet; it is required for  '
 calculation of RVCM. In the case of
 dispersion resins, the cup cannot be used.
 Weigh the sample in an aluminum dish.
 transfer the sample to the" tared viaL and
 accurately weigh it in the viaL After
•prepressnrization of the samples, condition
 mem for a minimum of 1 hour in the 90* C
 bath. Do not exceed 5 hoars.
  Nate—Some aluminum vial caps have e
 center section that must be removed prior to
•placing into sample tray. If the cap is not
 removed, the injection needle will be
        Suspension Resin Slurry and Wet
Cake Samples. Decant the water from a wet
cake sample, and turn the sample bottle
upside down onto a paper towel Wait for the
water to drain, place approximately 0.2 to 4.0
grams of the wet cake sample in a tared vial
(tared, including septum and aluminum cap)
and seal immediately. Then determine the
sample weight (±0.0001 g). All samples must
be prepressurized and then conditioned for l
hour at 90* C A sample of wet cake is used to
determine total solids (TS). This is required
for calculating the RVCM.
  B.2,3  Dispersion Resin Slurry and Ceon
Latex Samples. The materials should not be
filtered. Sample must be thoroughly mixed.
Using a tared vial (tared, including septum
and aluminum cap) add approximately eight
drops (
-------
           Federal Register / Vol. 47. No. 173  / Tuesday. September 7. 1982 /  Rules and Regulations
  Position 5—2000-ppm standard, freshly
prepared.
  Position 6—4000-ppm standard, freshly
prepared.
  Position 7—Sample" No. 7 (This is the first
sample of the day. but is given as 7 to be
consistent with the turntable and the
integrator printout)
  After all samples have been positioned.
insert the second set of 5O-, SOO-. 2000-. and
4000-ppm standards. Samples, including
standard*, must be conditioned in the bath of
90* C for 1 hour (not to exceed S hours).
  13.4 Start Chromatognph Program. When
•11 samples, including standards, have been
conditioned at 90* C for 1 hour, start the
analysis program according to the
manufacturer's instructions. These
instructions most be carefully followed when
starting and stopping a program to prevent
damage to the dosing assembly.
  &3J Determination of IS. For wet cake,
shitty, resin solution, and PVC latex samples.
determine IS for each sample by accurately
wetghm
timately 3 to 4 grams of
          i aluminum pan before and after
placing in a draft oven (105 to 110* C].
3nBfJf** must be dried to **««t«nt weight.
After first weighing, return the pan to the
oven for a abort period of tune, and then
reweigh to verify complete dryness. The TS
are thifft calculated as die  ft»^i sample
weight divided by initial sample weight
  9. Calibration. Calibration is to be
performed each a-hour period when the
natnanent is used. Each day. prior to running
auntes. the column should be conditioned
by ronmng two 2000-ppm standards from the
prevtoasday.
  9.1  Preparation of Standards. Calibration
standards are prepared as follows; Place  -'
lOOpl or about two equal drops of distilled
water in the sample rial then fill the vial
with the VCM/nitrogen standard, rapidly
seat the septum, and seal with the aluminum
cap. Use a %-in. stainless steel line from the
cylinder to me vial Do not use rubber or
tygon tubing. The sample line from the
cylinder must be purged (into a properly
vented hood) for several minutes prior to
fiHing the vials. After purging, reduce the
flow rate to 900 to 1000 cc/min. Place end of
tubing into vial (near bottom). Position a
aeptum on top of the vial pressing it against
the X*m. filling tube to minimize the size of
the veat opening. This is neceaaary to
mimhnixe mixmg air wiA the standard in the
vial. Each vial is to be purged with standard
far 90 seconds, daring which time the filling
1abe is gradually sfid to the top of the vial
Afier&e 90 seconds, the tube is removed
win te septum, simultaneously sealing the
vial Practice will be necessary to develop
food technique. Rubber glove* abouU be
womduring the above operations. The sealed
vial must then be pressurized for 80 seconds
using me vial prepressurizer. Test the vial for
httkagebypladatiadrapofwateronthe
septum at the needle bole.
  *2  Preparation of Chromatograph
Calibration Com.
                               Prepare two 50-. 500-, 2000-, and 4000-ppm
                             standard samples. Run the calibration
                             samples in exactly the same manner as
                             regular samples. Plot A«.the integrator area
                             counts for each standard sample, versus C,,
                             the concentration of vinyl chloride in each
                             standard sample. Draw a straight line through
                             the points derived by the least squares
                             method,           .        .      .
                               10. Calculations.
                               10.1  Response Factor. If the calibration
                             curve described in Section 9.2 passes through
                             zero, a response factor. Rf, may be used to
                             compute vinyl chloride concentrations. To
                             compute a response factor, divide any
                             particular A. by the corresponding  C*
                                                           Eq.  107-1
                              Where
                                   * Chroma tograph area counts of vinyl
                                 Crvc
                                         AsPa
                               Results calculated using these equations
                             represent concentration baaed on the total
                             sample. To obtain results based on dry PVC
                             content divide by TS.
                               \\. References.
                               l.BJ. Goodrich. Residual Vinyl Chloride
                             Monomer Content of Polyvinyl Chloride
                             Resins. Latex Wet Cake. Slurry and Water
                             Samples. EF. Goodrich Chemical Group
                             Standard Test Procedure No. 1005-E. B-F.
                             Goodrich Technical Center. Avon Lake. Ohio.
                             October 8.1979.
                               2. Berens, AJL The Diffusion of Vinyl
                             Chloride in Potyvinyi Chloride. ACS—
                             Division of Polymer Chemistry. Polymer
                             Preprints 15 (2)397.1974,
                               3. Berens. AJt The Diffusion of Vinyl
                             Chloride in Polyvinyl Chloride. ACS—
                             Division of Polymer Chemistry, Polymer
                                          750
                                                              iO •
                             Gas Chromatography. Journal of Applied
                             Polymer Science. W.3189-3172,1975. >
                               5. Mansfield. RJ\-The Evaluation of '
                             Henry's Law Constant (Kp) and Water
                             Enhancement in the Perkin-Ehner Multifract
                             F-40 Gas Chromatograph. BJ. Goodrich.
                             Avon Lake. Ohio. February 10,197&
    chloride for the sample.
   P.=Ambient atmospheric pressure, mm Hg.
   R,=Response factor in area counts per ppm
    VCM.
   T,=Ambient laboratory temperature. *K.
   M,=Molecularjveight of VCM, 62.5 g/
    mole.
   V,=Volume of the vapor phase, cms.
   R=Gas constant, (62360 on,) (mm Hg/
     mole) (*K).
   m=Sample weight, g.
   K»=Henry's Law Constant for VCM in
     PVC @ 90* C 6J2X10-»g/g/mm Hg.

   If the calibration curve does not pass
 through zero, the calibration curve must be
 employed to calculate each sample
 concentration unless the error introduced by
 using a particular Rf is known.
   1O2  Residual Vinyl Chloride Monomer
 Concentration, (C,^) or Vinyl Chloride
 Monomer Concentration. Calculate C^. in
 ppm or mg/kg aa follows:
             -  TS)  T
Eq.  107-2
Preprints 15 (2)503.1974.
  4. Berens, AJL. LB. Crider, CJ. Tomanek,
and J.M. Whitney. Analysis for Vinyl
Chloride in PVC Powders by Head—Space

  TS=«Total solids expressed as a decimal
    fraction.
  Tt^Equilibrium temperature, *K-
  K.S Henry's Law Constant for VCM in
    water @ 90* C. 7xiO-Tg/g/mm Hg.
  Assuming the following conditions are met.
these values can be substituted into Equation
107-2:
  P.—750 mm Hg.
  V,—Vial volume—sample volume (Fisher
    vials are 22.0 cm1 and Perkin-Ehner vials
    are 21.3 cm^.
  T,-23*Cor298'K.
  Tt=90*C6r363*K.



+ S.2S x 10"*(TS)(3S3) * 7.0 x 1
-------
                                      DRAFT
40 CFR  Part 61, Appendix B  ' DO NOT QUOTE OR CITE
Proposed 4/18/80
45 FR 26660 (may be start of standard)
Updated draft 7/23/82
                       METHOD 110.  DETERMINATION OF BENZENE
                              FROM STATIONARY SOURCES
             Introduction
                  Performance of this method should not be attempted by
                  persons  unfamiliar with the operation of a gas chroma-
                  tograph,  nor by  those who are unfamiliar with source
                  sampling, because knowledge beyond the scope of this
                  presentation is  required.  Care must be exercised to
                  prevent  exposure of sampling personnel to benzene,
                  a carcinogen.
             1.   Applicability and Principle
                  1.1   Applicability.  This method applies to the measure-
             ment of benzene in  stack gases from processes as specified
             in the regulations.   The method does not measure benzene
             contained in particulate matter.
                  1.2  Principle.  An  integrated  bag  sample  of  stack gas
             containing benzene  and  other organics  is  subjected to  gas
             chromatographic (GC)  analysis,  using a flame ionization
             detector (FID).
             2.  Range and Sensitivity
                  The range of this method is 0.1 to 70 ppm.  The upper
             limit  may be  extended by extending the calibration range  or
             by  diluting  the sample.
                                        110-1

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3.  Interferences
     The chromatograph columns and the corresponding  operating
parameters herein described normally provide an adequate
resolution of benzene; however, resolution interferences may
be encountered on some sources.  Therefore, the chromatograph
operator shall select the column and operating parameters best
suited to his particular analysis problem, subject to the approval
of the Administrator.  Approval is automatic provided that the  tester
produces confirming data .through an adequate supplemental analytical
technique, such as analysis with a different column or GC/mass
spectroscopy, and has the data. Available for review by the
Administrator.
4.  Apparatus
     4.1  Sampling (see Figure 110-1).  The sampling  train
consists of the following components:
     4.1.V  Probe.  Stainless steel, Pyrex* glass, or Teflon
tubing (as stack temperature permits), equipped with  a glass
wool plug to remove particulate matter.
     4.1.2  Sample Lines.  Teflon, 6.4-mm outside diameter,
of sufficient length to connect probe to bag.  Use a  new
unused piece for each series of bag samples that constitutes
an emission test anc| discard upon completion of the test.
*  Mention of any trade name or specific product does not
   constitute endorsement by the Environmental  Protection Agency.
                           110-2

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     4.1.3  Quick Connects.  Stainless steel, male  (2) ana
female (2), with ball  checks (one pair without),  located as
shown in Figure 110-1.
     4.1.4  Ted!ar or Alunrinized Mylar Bags.   100-liter
capacity, to contain sample.
     4.1,5  Bag Containers,  Rigid leakproof containers  for
sample bags, with covering to protect contents from sunlight.
     4,1.6  Needle Valve.  To adjust sample flow rate.
     4,1,7  Pump.  Leak-free, with minimum of 2-liters/min
ca^city.
     4,1,8  Charcoal Tube,  To prevent admission of benzene
and other organics to the atmosphere in the vicinity of
samplers,
     4,1,9  plow Meter,  For observing sample flow rate;
capable of measuring a flow range from 0.10 to 1.00 liter/min.
     4,1.10  Connecting Tubing,  Teflon, 6.4-mm outside
dtanieter, to assemble sampling train  (Figure 110-1).
     4,2  Sample Recovery.  Teflon tubing, 6.4-mm outside
diameter* is required to connect bag  to gas chromatograph
sample loop for sample recovery.  Use a new unused piece
for each  series of  bag samples that constitutes an emission
test and  discard upon conclusion of analysis of those bags.
     4.3' Analysis.   The following equipment is needed:
     4,3.1  Gas Chromatograph.  With  FID,  potentiometric
                                         /
strip  chart recorder, and 1.0-  to 2,0-ml sampling loop in
                           110-3

-------
FILTER (GLASS WOOL)

             , PROBE
      TEFLON
    SAMPLE LINE
VACUUM LIME
xaz—{r^ririrzr^T
    STACK WALL
            QUICK
          CONNECTS
            (MALE),
          V
 BALL
CHECKS
    v rrr
     FLOW METER
                          TEDLAR OR
                          ALUMINIZED
                          MYLAR BAG
                                            NO BALL
                                            CHECKS
                                            y
                            RIGID LEAK-PROOF
                               CONTAINER
                               CHARCOAL TUBE
                                                  PUMP
       Figure 110-1.  Integrated-bag sampling train. (Mention of trade names
       or specific products does not constitute endorsement by the Environ-
       mental Protection Agency.)
                           110-4

-------
automatic sample valve.   The chromatographic  system shall
be capable of producing a response to  0.1-ppm benzene
that is at least as great as the average noise  level.
(Response is measured from the average value  of the
baseline to the maximum of the waveform, while standard
operating conditions are in use.)
     4.3.2  Chromatographic Columns.  Columns as listed
below.  The analyst may use other columns provided that
the precision and accuracy of the analysis of benzene
standards are not impaired and he has available for review
information confirming that there is adequate resolution
of the  benzene  peak.  (Adequate resolution is defined as
an area overlap of not more than 10 percent of the benzene
peak by an  interferent peak.  Calculation of area overlap
is explained  in Appendix E, Supplement A:  "Determination
of Adequate Chromatographic Peak  Resolution.")
     4.3.2.1  Column A:  Benzene  in the  Presence of Aliphatics.
Stainless steel,  2.44 m  by 3.2 mm,  containing  10 percent
1,2,3-tris  (2-cyanoethoxy) propane  (TCEP) on 80/100
Chromasorb  P  AW.
      4.3.2.2  Column B:   Benzene with Separation of the
 Isomers of Xylene.  Stainless steel,  1.83 m  by 3.2 mm,  con-
 taining 5 percent SP 1200/1.75 percent Bentone 34 on  100/120
 Supelcoport.
                             110-5

-------
     4.3.3  Flow Meters  (2).   Rotameter  type,  100-ml/min
capacity.
     4.3.4  Gas Regulators.   For required gas  cylinders.
     4.3.5  Thermometer.  Accurate to 1°C, to  measure
temperature of heated sample loop at time of sample injection.
     4.3.6  Barometer.  Accurate to 5 mm Hg, to measure
atmospheric pressure around gas chromatograph during sample
analysis.
     4.3.7  Pump.  Leak-free, with minimum of 100-ml/min
capacity.
     4.3.8  Recorder.  Strip chart type, optionally equipped
with either disc or electronic integrator.
     4.3.9  Planimeter.  Optional, in place of disc or
electronic integrator, on recorder, to measure chromatograph
peak areas.
     4.4  Calibration.  Sections 4.4.2 through 4.4.5 are for
the optional  procedure  in Section 7.1.
     4.4.1  Tubing.   Teflon,  6.4-mm outside diameter,  separate
 pieces marked for each  calibration concentration.
     4.4.2  Tedlar or Aluminized Mylar Bags.  50-liter
 capacity, with valve; separate  bag marked  for each calibration
 concentration.
      4.4.3 Syringes.  1.0-pl  and  10-pl,  gas tight, individually
 calibrated to dispense  liquid benzene.
                            110-6

-------
     4.4.4  Dry Gas Meter, with Temperature and  Pressure
Gauges.  Accurate to t 2 percent, to meter nitrogen  in
preparation of standard gas mixtures, calibrated at  the
flow rate used to prepare standards.
     4.4.5  Midget Impinger/Hot plate Assembly.   To
vaporize benzene.
5.  Reagents
     Use only reagents that are of chromatographic grade.
     5.1  Analysis.  The following are needed for analysis:
     5.1.1  Helium or Nitrogen.  Zero grade, for chromatograph
carrier gas.
     5.1.2  Hydrogen.  Zero grade.
     5.1.3  Oxygen or Air.  Zero,grade, as required  by the
detector.
     5.2  Calibration.  Use one of the following options:
either 5.1.1 and 5.2.2, or 5.2.3.
     5.2.1  Benzene, 99 Mol Percent Pure.  Certified by the
manufacturer to contain a minimum of 99 Mol percent benzene;
for use in the preparation of standard gas mixtures as
described in Section 7.1.
     5.2.2  Nitrogen.  Zero grade,  for preparation of standard
gas mixtures as described  in Section 7.1.
     5.2.3  Cylinder  Standards  (3).  Gas mixture  standards
 {50-,  10-,  and  5-ppm benzene in nitrogen cylinders).  The tester
may use cylinder  standards to  directly prepare  a  chromatograph
                             110-7

-------
calibration curve as  described in Section  7.2.2,  if the
following conditions  are  met:   (a) The manufacturer certifies
the gas composition with  an accuracy of +_3 percent or better
(see Section 5.2.3.1).   (b) The manufacturer recommends  a
maximum shelf life over which the gas concentration does not
change by greater than +.5 percent from the certified value.
(c) The manufacturer affixes the date of gas cylinder prepa-
ration, certified benzene concentration, and recommended
maximum shelf life to the cylinder before shipment to the buyer.
     5.2.3.1  Cylinder Standards Certification.  The manufacturer
shall certify the concentration of benzene in nitrogen in each
cylinder  by  (a)  directly analyzing each cylinder and (b) cali-
brating his  analytical procedure  on the day of cylinder analysis.
To calibrate his analytical procedure, the manufacturer shall
use, as a minimum, a three-point  calibration curve.  It is
recommended  that the manufacturer maintain  (1) a high-concen-
tration  calibration  standard  (between 50  and 100 ppm) to prepare
his calibration  curve  by an appropriate dilution technique  and
 (2) a  low-concentration  calibration standard  (between 5 and
 10 ppm)  to verify the  dilution technique  used.   If the difference
 between the apparent concentration  read from the calibration
 curve and the  true concentration assigned to the low-concen-
 tration calibration  standard  exceeds 5 percent of  the true
 concentration, the manufacturer shall determine the source  of
 error and correct it,  then repeat the three-point  calibration.
                             110-8

-------
     5.2.3.2  Verification of Manufacturer's Calibration
Standards.  Before using, the manufacturer shall  verify
each calibration standard by (a) comparing it to gas mixtures
prepared (with 99 Nol percent benzene) in accordance with
the procedure described in Section 7.1 or by (b) having it
analyzed by the National Bureau of Standards.  The agreement
between the initially determined concentration value and the
verification concentration value must be within +, 5 percent.
The manufacturer must reverify all calibration standards on
a time interval consistent with the shelf life of the cylinder
standards sold.
     5.2.4  Audit Cylinder Standards (2).  Gas mixture
standards with concentrations known only to the person
supervising the analysis of samples.  The audit cylinder
standards shall be identically prepared as those in
Section 5.2.3  (benzene  In nitrogen cylinders).  The concen-
trations  of the audit cylinders should be:  one low-concen-
tration cylinder  in  the range of  5- to 20-ppm benzene, and
one  high-concentration  cylinder in the range of 100- to  300-ppm
benzene.  When available, the tester may  obtain audit  cylinders
by contacting:  Environmental Protection  Agency, Environmental
Monitoring and Support  Laboratory,  Quality Assurance Branch
 (MD-77),  Research Triangle  Park,  North Carolina  27711.
                              110-9

-------
If audit cylinders are not available at the Environmental
Protection Agency, the tester must secure an alternative source.
6.  Procedure
     6.1  Sampling.  Assemble the sample train as shown  in
Figure 110-1.  Perform a bag leak check according to
Section 7.3.2.  Join the quick connects as illustrated,  and
determine that all connections between the bag and the probe
are tight.  Place the end of the probe at the centroid of the
stack and start the pump with the needle valve adjusted  to
yield a flow that will more than half fill the bag in the
specified sample period.  After allowing sufficient time to
purge the line several times, connect the vacuum line to the
bag and evacuate the bag until the rotameter indicates no
flow.  Then reposition the sampling and vacuum lines and
begin the actual sampling, keeping the rate constant. At
all times, 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.  Protect
the bag container from sunlight.
     6.2  Sample Storage.  Keep the sample bags out of direct
sunlight.  Perform the analysis within 4 days of sample
collection.
     6.3  Sample Recovery.  With a new piece of Teflon
tubing  identified for that bag, connect a bag inlet valve

                           110-10

-------
to the gas chromatograph sample valve.   Switch  the valve
to receive gas from the bag through the sample  loop.
Arrange the equipment so the sample gas passes  from  the
sample valve to a 100-ml/min rotameter  with flow control
valve followed by a charcoal tube and a 1-in.  H20 pressure
gauge.  The tester may maintain the sample flow either by
a vacuum pump or container pressurization if the collection
bag remains in the rigid container.  After sample loop purging
is ceased, always allow the pressure gauge to return to  zero
before activating the gas sampling valve.
     6.4  Analysis.  Set the column temperature to 80°C  for
column A or 75°C for column B, and the  detector temperature
to 225°C.  When optimum hydrogen and oxygen flow rates have
been determined, verify and maintain these flow rates during
all chromatograph operations.  Using zero helium or  nitrogen
as the carrier gas, establish a flow rate in the range
consistent with the manufacturer's requirements for  satisfactory
detector operation.  A flow rate of approximately 20 ml/min
should produce adequate separations.  Observe the base line
periodically and determine that the noise level has  stabilized
and that base-line drift has ceased.  Purge the sample loop
for 30 sec at the rate 100 ml/min, then activate the sample
valve.  Record the injection time  (the position of the pen
on the chart at  the  time of  sample injection), the sample
number, the sample loop temperature, the column temperature,
                             110-11

-------
carrier gas flow rate,  chart speed, and  the  attenuator
setting.  Record the barometric pressure.  From the chart,
note the peak having the retention time  corresponding to
benzene, as determined in Section 7.2.1.  Measure the
benzene peak area, Am> by use of a disc  integrator, electronic
integrator, or a planimeter.  Record Am and  the retention
time.  Repeat the injection at least two times or until  two
consecutive values for the total area of the benzene peak
do not vary more than 5 percent.  Use the average value for
these two  total areas to compute the bag concentration.
     6.5   Determination of Bag Water Vapor  Content.  Measure
the  ambient temperature and barometric  pressure near the bag.
From a water saturation vapor  pressure  table, determine and
record  the water vapor content of the bag as a decimal figure.
 (Assume the  relative humidity  to be 100 percent unless a lesser
 value  is known.)
 7.   Preparation of Standard Gas Mixtures, Calibration, and
     Quality Assurance
      7.1  Preparation of Benzene Standard Gas  Mixtures.
 (Optional Procedure—delete if cylinder standards are used.)
 Assemble the apparatus shown in Figure  110-2.   Evacuate  a
 50-liter Tedlar or aluminized Mylar bag that has passed  a
 leak check (described in Section 7.3.2) and meter in about
 50  liters of nitrogen.  Measure the barometric pressure,
                             110-12

-------
 00
NITROGEN CYLINDER
                                                       HOT PLATE
                                    TEDLAR BAG
                                     CAPACITY
                  Figure 110-2. Preparation of standards (optional).
                              110-13

-------
the relative pressure at the dry gas  meter,  and the  temperature
at the dry gas meter.  While the bag  is  filling use  the 10-yl
syringe to inject 10 yl of 99+ percent benzene through the
septum on top of the impinger.  This  gives a concentration
of approximately 50 ppm of benzene.  In  a like manner, use
the other syringe to prepare dilutions having approximately
10- and 5-ppm benzene concentrations.  To calculate the
specific concentrations, refer to Section 8.1.  These gas
mixture standards may be used for 7 days from the date of
preparation, after which time prepare new gas mixtures.
(Caution:   If the new gas mixture standard is a lower concen-
tration than the previous gas mixture standard, contamination
may be a problem when a bag  is reused.)
     7.2  Calibration.
     7.2.1  Determination of Benzene Retention Time.  (This
section can be performed simultaneously with Section 7.2.2.)
Establish chromatograph conditions identical with those in
Section 6.4 above.   Determine  proper attenuator position.
Flush  the sampling  loop with zero  helium  or nitrogen and
activate the  sample valve.   Record the  injection time, the
sample loop temperature, the column  temperature, the carrier
gas  flow rate, the  chart speed,  and  the attenuator  setting.
 Record peaks  and detector  responses  that  occur in the absence
 of benzene.  Maintain conditions,  with  the  equipment  plumbing
 arranged identically to Section 6.3,  and  flush the  sample loop

                             110-14

-------
for 30 sec at the rate of TOO ml/min  with  one of the benzene
calibration mixtures.   Then activate  the sample valve.  Record
the injection time.   Select the peak  that  corresponds to
benzene.  Measure the distance on the chart from the injection
time to the time at which the peak maximum occurs.  This
distance divided by the chart speed,  is defined as  the  benzene
peak retention time.  Since it is quite likely that there will
be other organics present in the sample,  it is very important
that positive identification of the benzene peak be made.
     7.2.2  Preparation of Chromatograph Calibration Curve.
Make a gas chromatographic measurement of each standard gas
mixture (described in Section 5.2.3 or 7.1) using  conditions
identical with those listed in Sections 6.3 and  6.4.   Flush the
sampling loop 30 sec at the rate of 100 ml/min with one of the
standard gas mixtures and activate the sample valve.   Record
C_, the concentration of benzene injected, the attenuator
 . w
setting, chart speed, peak area, sample loop temperature,
column  temperature, carrier  gas  flow  rate, and retention time.
Record  the barometric pressure.  Calculate A£, the peak area
multiplied by the attenuator setting.  Repeat until two con-
secutive  injection  areas are within  5 percent, then plot the
average of those two  values  versus Cc-  When  the other standard
 gas mixtures have been similarly analyzed and plotted, draw  a
 straight line through the points derived  by the least  squares
                            110-15

-------
method.  Perform calibration daily,  or before  and after each
set of bag samples, whichever is more frequent.
     7.3  Quality Assurance.
     7.3.1  Analysis Audit.  Immediately after the  preparation
of the calibration curve and before the sample analyses,  perform
the analysis audit described in Appendix E, Supplement B:
"Procedure for Field Auditing GC Analysis."
     7.3.2  Bag Leak Checks.  While performance of this section
is required after  bag use,  it is also advised that it be per-
formed before bag  use.  After each use, make sure a bag did not
develop  leaks by connecting a water manometer and pressurizing
the  bag  to 5 to 10 cm H20  (2 to  4 in. HgO).  Allow to stand
for  10 min.  Any displacement in the  water manometer indicates
a leak.   Also,  check the rigid  container for leaks in this
manner.   (Note:  An  alternative  leak  check method is to
 pressurize the  bag to 5 to 10 cm H20  (2 to 4  in. H20) and
 allow to stand  overnight.   A deflated bag  indicates a leak.)
 For each sample bag  in  its rigid container, place a rotameter
 in line between the bag and the pump  inlet.   Evacuate the bag.
 Failure of the  rotameter to register  zero  flow when the  bag
 appears to be empty indicates a leak.
 8.  Calculations
      8.1  Optional Benzene Standards Concentrations.  Calculate
  each benzene standard  concentration (C  in ppm) prepared in
  accordance with Section 7.1 as  follows:

                            110-16

-------
     C   =  B(0.2706)Q03)
             m   T    760
                     B T
         -  vm  Q       m                          Eq.  110-1
            /ui.:?  w  Y" p
                    m    m
Where:
     B      -  Volume benzene Injected, yl.
     V      =  Gas volume measured by dry gas meter, liters.
     Y      =  Dry gas meter calibration factor, dimensionless.
     Pm     =  Absolute pressure of the dry gas meter, mm Hg.
     Tm     =  Absolute temperature of the dry gas meter, °K.
     0.2706 =  Ideal gas volume of benzene at 293° K and
               760 mm Hg liters/ml.
       o
     10     =  Conversion factor I (ppm) (ml )]/]/!.
     8.2  Benzene Sample Concentrations.  From the calibration
curve described in Section 7.2.2 above, select the value of
C  that corresponds to A_.  Calculate the concentration of
benzene in the sample (Cg in ppm) as follows:
     c   *    _CcPrTi                              Eq. 110-2
      s           C1'S
                            110-17

-------
Where:
     C   •  Concentration of benzene  indicated  by the gas
      c
            chromatograph, ppm.
     P   «  Reference pressure,  the barometric  pressure
            recorded during calibration, mm Hg.
     T*  •  Sample loop temperature at the time of analysis,  °K.
     Pj  •  Barometric pressure at time of analysis, mm  Hg.
     Tr  *  Reference temperature, the sample loop temperature
            recorded during calibration, °K,
     Swb P  Water vapor content of the bag sample, volume
            fraction,
 9, -Bibliography
     1,  feairheller, W,R,, A,M, Kemmer, B»J, Warner,  and
 D,Q, Douglas.  Measurement of Gaseous Organic Compound Emissions
 by Ga.§ Chromatography,   EPA Contract No. 68-02-1404, Task 33
 and  68-02-2818, Work Assignment 3.  January 1978.  Revised by
 EPA  August 1978,
      2.   Knoll, Joseph  E,, Wade H. Penny, M, Rodney Midgett.
 The  Use  of Tedlar Ba.gs  to Contain  Gaseous Benzene Samples at
 Source-Uvel  Concentrations,  Environmental Monitoring Series,
 EpA-600/4-78^057,   u,S,  Environmental  Protection Agency,
 Research Triangle Park, North Carolina.  October 1978.
      3.   Supelco, Inc.   Separation of Hydrocarbons.
 Bulletins 743A, 740C,  and 740D,   Bellefonte, Pennsylvania.
 1974,

                             110-18

-------
     4.  Carle Instruments,  Inc.   Current Peaks.  10:(1).
Fullerton, California.  1977.
     5.  Communication from  Joseph E.  Knoll.   Chromatographic
Columns for Benzene Analysis.   October 18, 1977.
     6.  Communication from  Joseph E.  Knoll.   Gas
Chromatographic Columns for  Separating Benzene from Other
Organics in Cumene and Maleic Anhydride Process Effluents.
November 10, 1977.
                               110-19

-------
40 CFR  Part 61, Appendix C
Final,  Promulgated 9/7/82
47 FR 39168
                        APPENDIX C - QUALITY ASSURANCE PROCEDURES

           PROCEDURE 1—DETERMINATION OF ADEQUATE CHROMATOGRAPHIC  PEAK RESOLUTION
              In this method of dealing with resolution, the extent to which
         one chromatographic peak overlaps another is determined.
              For convenience,  consider the range of the elution curve of each
         compound as running from -2a to +2c.  This range is used  in other
         resolution criteria, and it contains 95.45 percent of the area of a
         normal  curve.  If two peaks are separated by a known distance, b, one
         can determine the fraction of the area of one curve that  lies within
         the range of the other.  The extent to which the elution  curve of a
         contaminant compound overlaps the curve of a compound that is under
         analysis is found by integrating the contaminant curve over the limits
         b-2o  to b+2cr , where a  is the standard deviation of the sample
         curve.
              This calculation can be simplified in several ways.   Overlap can
         be determined for curves of unit area; then actual areas  can be
         introduced.  Desired integration can be resolved into two integrals
         of the normal distribution function for which there are convenient
         calculation programs and tables.  An example would be Program 15 in
         Texas  Instruments  Program Manual ST1, 1975, Texas  Instruments, Inc.,
         Dallas, Texas  75222.
                                         Cl-l

-------
        b+2ci
       f      l!n         f
            >c/dt.-i. I
      J                 V2n J
                              .
       b-2as                 b-2as
                             ~
The following calculation steps are required:
1.   2(7S = ts//2 In 2
2.   ac = tc/2V2 In 2
3.   X! = (b-2as)/ac
4.   x2 =
                                            . *
                r
       ,) = i le
            ^J.
5.   Q(Xi)  = -^ le\fc  /dx
                 *1
          .-Lp
           V2n I
               ^
                    -v2
6.   Q(x2) = --   eV7" /dx
7.   I0 s Q(Xi)  -  Q(x2)
8-   Ao=IoVAs
9.   Percentage  overlap  = A  x ipO ,
where:
     A  = Area of the sample peak of interest determined by electronic inte-
          gration or by the formula A  = h t .
     A  = Area of the contaminant peak, determined in the same manner as A .
      b = Distance on the chromatographic chart that separates the maxima of
          the two peaks.
     HS = Peak height of the sample compound of interest, measured from the
          average value of the baseline to the  maximum of the curve.
     *In most instances,  Q(x2)  is  very small  and may be neglected.
                                 Cl-2

-------
     tg = Width of sample peak of interest at 1/2 peak height.
     tc = Width of the contaminant peak at 1/2 of peak height.
     a  = Standard deviation of the sample compound of interest elution
          curve.
     QC = Standard deviation of the contaminant elution curve.
  Q(xt) = Integral of the normal distribution function from xl to infinity.
  Q(x2) = Integral of the normal distribution function from x2 to infinity.
     IQ = Overlap integral.
     A  = Area overlap fraction.
     In judging the suitability of alternate GC columns or the effects of
altering chromatographic conditions, one can employ the area overlap as the
resolution parameter with a specific maximum permissible value.
     The use of Gaussian functions to describe chromatographic elution curves
is widespread.  However, some elution curves are highly asymmetric.   In cases
where the sample peak is followed by a contaminant that has a leading edge
that rises sharply but the curve then tails off, it may be possible to define
an effective width for t  as "twice the distance from the leading edge to a
perpendicular line through the maxim of the contaminant curve, measured along
a perpendicular bisection of that line."
                                  Cl-3

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Federal Register / Vol. 47, No. 173 / Tuesday. September 7. 1982  / Rules and Regulations


                         Procedure 1—Determination of Adequate
                         Chromalographic Peak Resolution

                           In this method of dealing with resolution.
                         the extent to which one chromatographic
                         peak overlaps another is determined.
                           For convenience, consider the range of the
                         elation curve of each compound as running
                         from -2
-------
          Federal Register / Vol. 47, No. 173 / Tuesday. September 7,1982  /  Rules and Regulations
       />    s/.t2 \           p  i     \          r/a\
       t      (   c i          I  I2£  i          I  te l
-i-  I     eV^/dt = ^  I eV^/dx - J^  JaV   L

    c  b-20                   b-2o.              b+2ff.
The following calculation steps  are required:1

1.  2ffs  = t$/«7 in 2

2.  oc = tc/2,/rin~Z

3.  xt = (b-2ffe)/a.
               5   w

4.  x2 = (b*2o.)/or
               5   C
                                                                            In judging the suitability of alternate GC
                                                                           columns or the effects of altering
                                                                           chromatographic conditions, one can employ
                                                                           the area overlap as the resolution parameter
                                                                           with a specific maximum permissible value.
                                                                            The use of Gaussian functions to describe
                                                                           chromatographic elution curves is
                                                                           widespread. However, some eiution curves
                                                                           are highly asymmetric. In cases where the
                                                                           sample peak is followed by a contaminant
                                                                           that has a leading edge that rises sharply but
                                                                           the curve then tails off. it may be possible to
                                                                           define an effective width for t. as "twice the
                                                                           distance from the leading edge to a
                                                                           perpendicular line through the maxim of the
                                                                           contaminant curve, measured along a
                                                                           perpendicular bisection of that line."

            -LC^
            vaij
                **i
                           dx
6.  Q(xa) » -^
          Q(xt) - Q(x,)
8.  A.
9.  Percentage overlap = Afl x  100  ,
where:
     A  « Area of the sample  peak of interest determined by electronic  inte-
       s    gration or by the formula A$ * h,^-

     AC  « Area of th« contaminant peak, determined in the same manner as  Af.

       b  * Distance on the  chromatographic chart  that separates the maxima of
           the two peaks.

     H  » Peak height of the  sample compound  of  Interest, measured  from the
      t - »
           average value  of the baseline to  the maximum of the  curve.

           Width of  sample peak of Interest at 1/2 peak height.
      t  * Width of  the contaminant peak  at 1/2 of peak height.

      o  * Standard  deviation of the  sample compound of Interest elution
       s   curve.

      a  = Standard  deviation of the  contaminant elution  curve.

          •• Integral  of* the normal  distribution function  from xt to infinity.

   Q(x2) = Integral  of the normal  distribution function  from x2 to infinity.

      I  s Overlap Integral.
       o
      A  = Area overlap fraction.
       o
      *In most instances,  Q(x2) 1s very small  and may be neglected.

     MO CODE MM-M-C

                                                   Cl-5

-------
40 CFR  Part 61, Appendix  C
Final ,  Promulgated
47 FR             PROCEDURE 2-PROCEDURE FOR FIELD AUDITING GC ANALYSIS
             Responsibilities of audit supervisor and analyst at the source
        sampling site include the following:
             A.  The audit supervisor verifies that audit cylinders are stored
        in a  safe location both before and after the audit to prevent vandalism.
             B.  At the  beginning and conclusion of the audit, the analyst
        records each cylinder number and pressure.   An audit cylinder is never
        analyzed when the  pressure drops below 200  psi.
             C.  During  the audit, the analyst performs  a  minimum of two
        consecutive analyses of each audit cylinder gas.   The audit must be
        conducted to coincide with the analysis  of  source  test samples,  normally
        immediately after  GC calibration and prior  to sample analyses.
             D.  At the  end of audit analyses, the  audit supervisor requests
        the calculated concentrations from the analyst and compares the  results
        with  the actual  audit concentrations.  If each measured  concentration
        agrees  with the  respective actual  concentration  within +_10 percent, he
        directs the analyst to begin analyzing source samples.   Audit
        supervisor judgment and/or supervisory policy determine  action when
        agreement is  not within  +10 percent.  When  a  consistent  bias  in  excess
        of 10 percent is found,  it may be possible  to proceed with the sample
        analysis,  with a corrective factor to  be applied to  the  results  at a
        later time.   However, every attempt should  be made to locate  the cause
        of the  discrepancy,  as it may be misleading.   The  audit  supervisor
        records each  cylinder number, cylinder pressure  (at  the  end of the
        audit), and all  calculated concentrations.   The  individual  being audited
                                       C2-1

-------
must not under any circumstance be told actual audit concentrations
until calculated concentrations have been submitted to the audit
supervisor.
                               C2-2

-------
                          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
     4.  Guaranteed arrival date for cylinders_
     5.  Planned shipping date for cylinders	
     6.  Details on audit cylinders from last analysis
                                            Low Cone.     High Cone
         a.  Date of last analysis          	     	
         b.  Cylinder number                	     	
         c.  Cylinder pressure, psi         	     	
         d.  Audit gas(es)/balance gas      	     	
         e.  Audit gas(es), ppm             	     	
         f.  Cylinder construction          	     	
                                 C2-3

-------
PART B   To be filled  out  by audit  supervisor

     1.   Process  sampled	
     2.  Audit  location
     3.   Matte  of Individual  audit_

     4.   Audit date
     5.  Audit results
                                                  Low Cone.   High  Cone,
                                                  Cy1i nder    Cy1i nder
          a.   Cylinder  number

          b.   Cylinder  pressure  before
              audit,  ps1

          c.   Cylinder  pressure  after
              audit,  psi

          d.   Measured  concentration, ppm
              Injection #1*
              Injection #2*
              Average

          e.   Actual  audit concentration, ppm
              (Part A,  6e)

          f.   Audit accuracy*
              Low Cone. Cylinder
              High Cone.  Cylinder
              Percent accuracy »              '                 *  10°

          g.  Problems detected (if any
    Results of two consecutive injections that meet the sample analysis
    criteria of the test method.
                               C2-4

-------
           Federal Register  /  Vol.  47. No. 173 / Tuesday. September 7. 1982 /  Rules and Regulations
Procedure 2—Procedure for Held Auditing
GC Analysis
  Responsibilities of audit supervisor and
analyst at the source sampling site include
the following:
  A. The audit supervisor verifies that audit
cylinders are stored in a safe location both
before and after the audit to prevent   '  ,
vandalism.
  E At the beginning and conclusion of the
audit the analyst records each cylinder
number and pressure. An audit cylinder is
never analyzed when the pressure drops
below 200 psi.
  C During the audit the analyst perform* a
minimum of two consecutive analyses of
each audit cylinder gas. The audit must be
conducted to coincide with the analysis of
source test samples, normally immediately
after GC calibration and prior to sample
analyses.
  0. At the end of audit analyses, the audit
supervisor requests the calculated
concentrations from the analyst and
compares the results with the actual audit
concentrations. If each measured
concentration agrees with the respective
actual concentration within ±10 percent he
directs the analyst to begin analyzing source
samples. Audit supervisor judgment and/or
supervisory policy determine action when
agreement is not within ±10 percent When a
consistent bias in excess of 10 percent is
found, it may be possible to proceed with the
sample analysis, with a corrective factor to
be applied to the results at a later time.
However, every attempt should be made  to
locate the cause of the discrepancy, as it  may
be misleading. The audit supervisor records
each cylinder number, cylinder pressure (at
the end of the audit), and all calculated
concentrations. The individual being audited
must not under any circumstance be told
actual audit concentrations until calculated
concentrations have been submitted to the
audit supervisor.

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
  4. Guaranteed arrival date for

  5. Planned shipping date for
cylinders	
  6. Details on audit cylinders from last
analysis
j Low cone


c. Cyfindtr prvmm, pti 	 — 	
|

•JUJNO COOK IMP 10 M
                                               C2-5

-------
         Designation: 0 1475 - 60 (Reapproved 1980)"'
         Standard Test Method For

         DENSITY OF PAINT, VARNISH, LACQUER,  AND RELATED
         PRODUCTS1

Thi* Mutdard a iuueJ under ihe fixed dcsif nation n W7J, ihc number immediately foliooinf the designation indium the
 tit ri~ original adepluxi 01. in ib* uue ol revision. ih< year oflast revision. A number in parentheses indicates the year of bun
 ei-oval.
/':/> mnhad kjs Am? aparottd/tr iur by axtittuet of iJtr Deportmtni of Dffrme (e rtfloce Method 4 1 84.1 of Ftdtral Tea
tfri/HM/ SiaxJarii So. 1 41 A a»dffr litsutf in .Ac DoO Indtx of Sp*cfieaiioiu and Siwidardt
              cJunfe».»cr; made ihrouchout ic Ocuher I9MO.
 t. Scope
   l.l This method covers the measurement of
density of paints, varnishes, lacquers, and ccm-
ronents  thereof, other than pigments, when in
 ;luid form.  It is panicularty applicable  where
 :hc fluid has too  high a  viscosity or where a
 omponeni  is too volatile for a specific gravity
         determination.
  Null I --The .-ncthod provides for the ma.iimuro
...curacy required for UJing power determinations.
•/. IN et^uaily well suited for work in which less accu-
:a."> is reuuireU. by ignoring the directions for recal-
       iind ctMUideraiion of terr.pvraiuK difl'eren-
   . by ut.mg ihe conuiner is
 1. Dcfinitioo
   2.1 density* ihe mass v*«ght in vacuo( of a
 T.ii volume of the liquid at any given tcmper-
 iiure. In ihis  method,  it is expressed  as  the
 • eight  in grams per cubic milliiiue. or «is ;.he
  e:t:hu in pour..i:> avoirdupois, of one U. S.
 atlon  measure >. el the iunie container at a stancarJ ;em-
 •  ijiure »2.i;C;  or a! an agrccd-upon icn.pcr-
 .  .::.'. is  '.her. deicrtnincvj. and  ijenM'.v oi' the
   ;;;cnt> (akeaccatcil Balance, or a
room of reasonably constant temperature and
humidity are desirable.

 5. Calibration of Pycnometcr or  Cup
   5.1  Determine the volume of the  container
 at the specified temperature by employing the
 following steps:
   ' Thi- method IN undei the junviiau.n of ASTM Com-
 nutter 0-i od Paint .mii RrUict! (.•»*une> jr,U Maieriat*.
   (. urnni cJinoii approve*! Sepi  I", i'ux'i Oricmjily iv-ueJ
  •'<• Rcpui-rv D u:'5 • ."T
                                       D1475-1

-------
                                              D147S
  5.1.1  Clean and dry the container and bring
it to constant weight. Chromic acid (see 5.1.1.1)
cleaner  and nonresidual solvents may be used
with glass containers, and solvents with metal
containers. For maximum  accuracy,  rinsing.
drying,  and weighing must be continued until
the difference between two successive weigh-
ings does not exceed 0.001 % of the weight of
the container.  Fingerprints on the container
will change the weight and most  be avoided.
Record  the weight, Af, in grams.
  5.1.1.1 Chromic acid  cleaning solution is
corrosive to skin, eyes and mucous membranes
and can cause severe burns. Avoid contact with
eyes, skin or dothing. In making dilute solu-
tion, always add acid to water with care. In
case of-contact, flush skin with water, using a
shower  if exposure is severe. Bush eyes for IS
minutes with  copious amounts of water. Im-
mediately call a physician.  Remove dothing
immediately and wash before  reuse. Chromic
acid cleaning  solution is a strong oxidizer.
Avoid contact with  organic or reducing sub*
Uanccs  as  a fire could results. See Supplier's
Material Safety Data'Sheet for farther infor-
mation.
  5.1.2  Fill the container with freshly boiled
distilled water at a temperature somewhat be-
low that specified. Cap the container, leaving
the overflow orifice open. Immediately remove
excess overflowed water or water held in de-
pressions by wiping dry with absorbent mate-
rial. Avoid ocdudtng air bubbles in the con-.
tainer.
  5.1,3  Bring  the container and contents to
specified temperature. Use the constant-tem-
perature bath or room if necessary. This  will
cause further  slight flow of water from the
overflow orifice due to  the expansion of the
water with the rise of the temperature.
   5.1.4  Remove the excess overflow by wiping
carefully with  absorbent  material,  avoiding
wicking of water out of orifice, and immedi-
ately cap  the overflow  tube where such  has
been provided. Dry the outside of the con-
tainer,  if necessary, by wiping with absorbent
 material. Do not remove overflow which occurs
 subsequent to the first wiping  after attainment
 of the  desired temperature (Note 3). Immedi-
 ately weigh the filled container to the nearest
 Ondl^ of its weight  (Note  4),  Record  this
 weight. .V. in grams.
  NOTT 2— Handling the container with bare hands
will increase the temperature and cause more over-
flow from the overflow orifice, and will also lean
fingerprints; hence, handling  only with tonp and
with hands protected by dean, dry. absorbent matt-
rial is recommended.
  NOT* 4— Immediate and rapid weighing of U*
filled cnuainei is recommended here to minimize
lots of weight due to evtoontion of the water through
orifice*, and from overflow subsequent to the Tint
wiping  afler attainment of temperature where ibis
overflow is not retained within a capped endosute.

  5.1 J Calculate the container volume as fol-
lows:
where:
»  • volume of container, mL.
.V - weight of container and water, g (5.1.4).
M - weight of dry container, g (5.1.1), and
q  - absolute density of water at specified tem-
      perature, g/mL (see Table 1).
  5.1.6 Obtain the mean of at least three de-
terminations of » to provide the value of V
required in 6.2.

6. Procedure
  6.1  Repeat the steps in Section 5, substitut-
ing  the sample fur the distilled water and *
suitable nonresidual solvent for the acetone or
alcohol (see  5.1.2 and Note  5). Record the
weight of the filled. container.  W, and the
weight of the empty container, w, in grams.
  NorE 5— Trapping of paint liquids in ground
glass or metal joints is liVery to result in high valuet
of density which appear to increase with the viscosity
and  density of the material; such errors should be
minimized by firm seating of the joints.
   6.2 Calculate the density in grams per nul-
lilitre as follows:
 where:
 Dm » density, g/mL.
   6.3 Calculate the density in pounds per gal-
 lon as fellows:
 where:
 D - density. Ib/guL
 Km 8.3455* (Note 6). and
 V — volume of container. mL (see 5.1.6).
    Sort .'•—The factor V. S.JWSS. is calculated from
 volume'wetcht rcU'.-or.yhip as follow*:
                                      D1475-2

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         Designation: 0 2369 - 81
         Standard Test Method  for

         VOLATILE  CONTENT OF COATINGS'

This standard is issucj under the fixed designation D 236"»: the number immediateN following the designation indicate'*
year of original adoption or. in the case of revision, the year of the last revision. A number in parentheses indicates ihe >e*
of last reapproval. A superscript epsilon («) indicates an editorial change since the last revision or reapcrovai.
This method ha* t*vn approved for u.\e Ay agencies of the Department of Defence to replace Method -KM I. / of Federal I''
Method Standard No  1414 and for lilting in the DoD Index of ' Spfcificatmnn and Standards.
1.  Scope
   1.1 This  method describes  two procedures
for the determination  of the weight  percent
volatile content of solvent reducible and water
reducible coatings. Test specimens are healed
al 110°C ± 5°C  for 60 min, or optionally for
20 min. Although the technique  used is  the
same, residence times in the oven differ. The
two procedures are designated as follows:
   I.I.I  Procedure  A—Volatile  Content  of
Coalings Determined for 20 min  at 110°C ±
5°C.
   1.1.2 Procedure  R   (Preferred)-  Volatile
Content of Coatings Determined for 60 min at
1IO°C±5°C.
   1.1.2.1  Choice of and preference for 60 min
at 1 IO°C ± 5°C  as a general purpose method
is based on the precision data presented in ihese
methods that  was obtained on both solvent
reducible and water reducible coalings (see Sec-
tion 7). These coatings (single package, heat
cured)  are  commonly  applied in  factories to
automobiles, metal containers, flat (coil) metal
and large appliances and many  other metal
parts. Procedure B is presumed applicable, sub-
ject to further  precision studies, to most kinds
of paints and related coatings intended for
either ambient or baking film formation, except
where substantial amounts of volatiles may be
consumed or produced in chemical reactions
during film formation.  If an oven residence
time of 20  min  at  110°C ± 5°C is used the
analyst  must recognize  that poorer precision
was obtained using Procedure A  (see Section
7).
   NOTE I—Testing at I IO°C ± 5CC for 20 rain was
utilized tor the establishment of the original method
in 1965. Precision data are not available and mayao1
have been properly generated at the time. The nu*
paints tested then were all solvent reducible. Tie*
conditions, 20 min at 110'C ± 5"C. are no Ion?*
satisfactory for the determination of volatile com*
of many coatings currently being listed in 1980. *•'
ler reducible and  solvent reducible coatings vttt
tested in the  development of the present method *
110°C  ± 5°C for 60 min  and 20 min for wtotf
precision data have been generated.
   1.2 This method does not cover multi-pa^'
age coalings wherein one or more parts may.*1
ambient conditions, contain liquid coreaciaflis
that are  volatile until  a chemical reaction 1*
occurred with another component of the mulu-
package coating.
   1.3 This method may  not be applicable w
all types of coalings such as printing inks. U"'
other procedures may be substituted with mu-
tual agreement of the producer and user.  S«
Note 5.

2. Applicable Documents
   2.1 A STM Standards:
   D343 Specification for 2-Elhoxyethyl Ace-
     tate-
   D 362 Specification for Industrial Grade Tol-
     uene"
   D 1193 Specification for Reagent Water'
   E 145 Specification for Gravity Convection
   1 These methods are under the jurisdiction of
 Committee D-1 on Paint and Related Coatings and Maief""
 and arc the direct responsibility of Subcommittee Oil 2' °*
 Chemical Analysis of Paint anil Paint Materials.
   Current edition approved June 26. 1981 Published yf
 lemher I'M I. Originally published as  D 2W 65 T. La"
 previous edition  D UW KO.
   • Annual Book of ASTM Standards. Pan 29.
   1 Annual Honk of 1 STM Standards. Parts :f). 21. -- A
 :<). 111. U. .17. 40. and 43
                                    D2369-1

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                                              D2369
     and Forced- Ventilation Ovens4
   £ 180 Recommended Practice for Develop-
     ing Precision Data on ASTM Methods for
     Analysis and Testing of Industrial Chem-
     icals5
   3.1 Forced Draft Oven, Type HA  or Type
  «g as specified in Specification E 145.
   3.2 Svringe. 5 mL. capable of dispensing the
        under test at sufficient rate  that  the
        i can be dissolved in  the solvent (see
 5.2).
   3 j Weighing or Dropping Bottle.
   3.4 Test Tube, with new cork stopper.
   3.3 Aluminum Foil Dish, 58 mm in diameter
 by 18 mm high with a smooth bottom surface.
 piecondition the dishes for 30 min in an oven
 „ |iO°C ± 5"C and store in a desiccator prior
 nose.
  41 Purity  of  Reagents — Reagent  grade
 chemicals shall be  used in  all tests. Unless
 otherwise indicated, it is intended that all re-
 agents shall conform to the specifications of the
 Committee on Analytical  Reagents of the
 American Chemical Society, where such spec-
 ifications are available. s Other grades may be
 used, provided it is ascertained that the reagent
 is of sufficiently high purity  to permit its use
 without lessening the accuracy of the determi-
 nation.
  42 Purity of Water — Unless otherwise indi-
 ctted, references to water shall be understood
 to mean Type II reagent grade water conform-
 ing to Specification O 1 193.
  4.3 Toluene,  technical grade. Specification
 D362.
  4.4 2-Eihoxyethyl Acetate, technical grade,
 Specification D 343.
  NOIT 2 — The solvents ami samples used in ihese
 awtnotis may. under some conditions, be hazardous.
 Refer to the manufacturers Material Safety Data
 Sheet for specific handling and safety precautions.
Safe laboratory handling procedures and all appli-
 cable U.S. Occupational Safety and Health Act reg-
 ulations are to be followed in the handling of samples
and solvents.

5. Procedure
  5. 1  Mix the sample, preferably on a mechan-
ical shaker or roller, until homogeneous. If air
bubbles become entrapped, stir by hand until
the air has been removed.
  5.2 Using an appropriate weighing container
(4.2. 4.3, or 4.4, with the syringe preferred for
highest precision), weigh to I mg, by difference,
a specimen of 0.30 ± 0.10 g tor  coatings be-
lieved to have a volatile content  less than 40
weight  % or a specimen of 0.50 ± 0.10 g for
coatings believed to have  a volatile content
greater than 40 weight %,  into a tared alumi-
num foil dish (4.5) into which has been added
3 ± 1  mL  of  suitable solvent (3.1, 3.2 or 3.3).
Add the specimen dropwise, shaking (swirling)
the dish to disperse the specimen completely in
the solvent. If the material forms a lump  that
cannot be dispersed, discard the specimen and
prepare a new one.  Similarly prepare a dupli-
cate.
  NOTF 3—If  the specimen cannot be dispensed in
the  solvents listed (31. 3.2 or  3.3)  a com pan hie
solvent may be substituted provided  it is no less
volatile than 2-ethoxyethyl acetate (3.3).
  5.3 Procedure A—Heat the aluminum foil
dishes containing the dispersed specimens in
the forced draft oven (4.1) for 2U nun at 110°C
±5eC.
  5.3.1 Caution—Provide  adequate  ventila-
tion, consistent with accepted laboratory prac-
tice, to prevent solvent vapors from accumulat-
ing to a dangerous level.
  5.4 Procedure B—Heal the aluminum foil
dishes containing the dispersed  specimens in
the forced draft oven (4.1) for 60 min at 1 IO°C
± 5°C. Caution: See Section 5.3.1.
  5.5 Remove the dishes from the oven, place
immediately in a desiccator,  cool  to ambient
temperature and weigh to t mg.
  NOTE 5—(f  unusual decomposition or degrada-
tion of the specimen occurs during heating, the actual
lime and temperature used to cure the coaling in
practice may be substituted for the time and temper-
ature specified  in  this method,  subject to mutual
agreemem of producer and user.

6, Cakulatioas
  6.1  Calculate the percent volatile matter in

  '  Annual Book  of ASTM Standards. Parts 39 and 41.
  1  .Aiumal Book  of 4 STM Standards. Part 30.
  *  "Reagent Chemicals. American Chemical Society Spec-
ifications. Am. Chemical Sue. Washington. U C Fur sug-
gestion* on the testing of reagents not listed by the American
Chemical Society, see "Reagent Chemicals and Standards."
by Joseph Rosin.  D. Van Most/and Co.. Inc.. New York. N.
Y. and the "United States Pharmacopeia."
                               D2369-2

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                                                 D2369
the liquid coating as follows:
 Volatile matter, % -  100 - [((W< - W^jS) x IOOJ
where:
 W\  = weigh I of dish.
 Wi  — weight of dish plus specimen after heat-
        ing, and
5   » weight of specimen.
  6.2  The percent of nonvolatile matter in the
coating may be calculated by difference as
follows:
    Nonvolatile matter » 100 - volatile matter

7. Precision
  7.1  Procedure A (20 min at 110°C ± 5°C):
  7.1.1 The precision estimates are based on
an interlaboratory study7 in which one operator
in each of 15 laboratories analyzed in duplicate
on two different days seven samples of water-
based paints and eight samples of solvent-based
paints containing between 35 % and 72 % vol-
atile  material The paints were commercially
supplied. The results were analyzed statistically
in  accordance  with  Recommended  Practice
E 180, and the  within-laboratories coefficient
of variation was found to be 1.5 % relative at
 193 degrees of freedom and the between-labo-
ratoncs coefficient of variation  was 2.5 % rela-
tive at 178 degrees of freedom.  Based on these
coefficients the  following criteria  should  be
used for judging the acceptability of results at
the 95% confidence level.
  7.1.1.1 Repeatability—Two results  each the
mean of duplicate determinations, obtained by
the same operator on different days, should be
considered suspect if they differ by more than
2.9% relative.
  7.1.1.2 Reproduability—Jwo  results,  t^ii
the mean of duplicate determinations, obtained
by operators in different laboratories should be
considered suspect if they differ by more than
7.1% relative.
  7.2  Procedure B (60 min at. 1 10°C ± 5°C):
  7.2. 1 The precision estimated for tests at 60
min at 1 10°C  ± 5°C are based on an interlab-
oratory study7 in which one operator in each of
15  laboratories analyzed in  duplicate on two
different days seven samples of water-based
paints  and eight samples  of  solvent-based
paints containing between 35 % and 72 % vol-
atile material. The paints were commercially
supplied. The results were analyzed statistically
in  accordance with Recommended Practice
E 180, and the within-laboratories coefficient
of variation was found to be 0.5 % relative at
213 degrees of freedom and the between-labo-
ratories coefficient of variation was 1 .7 % rela-
tive at 198 degrees of freedom. Based on these
coefficients, the following criteria should be
used for judging the acceptability of results at
the 95 % confidence  level.
  7.2. 1. 1 Repeatability— Two results, each the
mean of duplicate determinations, obtained by
the same operator on different days should be
considered suspect if they differ by more than
1.5% relative.
  7.2.1.2 Reproducibility—two  results,  each
the mean of duplicate determinations, obtained
by operators in different laboratories should be
considered suspect if they differ by more than
4.7 % relative.
   'Supporting data are available on loan  from
 Headquarters. 1916 Race St.. Philadelphia, Pa. 19103. Re-
 quest RRiDOl - 1026.
   The American Society for Testing and Materials takes no position respecting the validity of any patent righti asserted*
connection with any item mentioned in this standard. Users of this standard are expressly advised that determination of the latidto?
of any such patent rights, and the risk of in/'ringement of such rights, are entirely their own responsibility.

   This standard is subject to revision at any lime by the responsible technical committee and must be reviewed every five yeft
and if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for adduiomi
standard* and should be addressed to A STM Headauorters. Your comments will receive careful consideration at a meeting aftht
responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you shot*
make your views known to the ASTM Committee on Standards, /*/« Race St.. Philadelphia. Pa.  19101. which will schedule »
further hearing regarding your comments. Failing satisfaction there, you may appeal to the A STM Board of Directors.
                                       D2369-3

-------
ih«liiY of Subcommittee DOU) on'Chemical Analy«i
                                            of Paint knd Patnt Materials.
                                               Current edition apnnwed May 2SWI$79. Puhlithed JjK
                                            I«79.
                                               ' Annual Book of ASTM SieitJardi. Pan 29.
                                               1 Amuat Ho*>k of ASTM Sunwards. Pmn 42.
                                               ' Porapak 0® i* * trademark of Waters A»ocialev lac..
                                            Miifrri MOM. ami h*< been found satisfactory, i'orapax Q£
                                            i$ available from Waters Vdoaaiei and most |»« chromaio-
                                            f raphic tup?lie* dwtnbulorv *uch at Arnpec Co.. P. 0. 3f>k
                                            44. Ann -\rS>f. Mich . or Supcktt Inc.. Belltftwte. Ha.
                                             D3792-1

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                                              03792
(oversight). At the end of this period of time,
heat the column to 250°C (the maximum tem-
perature for this packing) at  a  5°C/min rate
tad bold at this temperature for several hours.
Cool  the column to room temperature and
connect the e»h'"m  detector.  Reheat the col-
umn to 2SO*C at 5'C/nin to observe if there
is epj"q
-------
D3792
W.   ™  weight of dimethyl formamide.
AH,O  ~  area of water peak,
A,    -  area of 2-propanol peak, and
         weight % water in DMF
                   100
   7.2.4 If Karl Fischer titration  is not avail-
able, the following procedure may be used to
obtain a reasonable estimate of the  response
factor
   7.2.4.1 Inject the same size aliquot of DMF
and 2-propanol mixture,  but without added
water, as a blank. Note the area of the water
peak in the blank.
   7.2.4.2 The response factor for water is  cal-
culated by means  of the following equation:

               R-
basis. Use of an electronic integrator is recom-
mended to obtain the best accuracy and preci-
sion. Howe\ er, triangulation, pbnimeter. paper
cut out,  or  ball and disk integrator  may be
used.
  9.2 Determine the water concentration in
the paint by means of the following equation:
                         W, x 100
 where:
 R     -  response factor.
 If,.   —  weight of 2-propanol,
 WH.O "  weight of the water,
 A,    -  area of 2-propanol peak.
 AHJO  -  area of the water peak, and
 B     -  area of the water peak the black.

 8. Procedure
    8.1 Weigh  to the nearest 0.1  mg  0.6  g  of
 water-reducible paint (see Note 2) and 0.2 g of
 2-propanol into a  septum vial. Add  2-ml  of
 dimethylformamide into the vial Seal the vial.
  Prepare a blank containing the 2-propanol and
 dimethylformamide but no paint.
    NOTE 2—Check each paint system to be analyzed
  for interfering peaks.  Coalescing agents do not inter-
  fere with this determination.
    8.2 Shake the vials on a wrist action shaker
  or other suitable device for IS min. To facilitate
  settling of solids allow the samples to stand for
  5 min just  prior  to injection into the  chro-
  matograph. Low speed ccntrifugation may also
  be used.
    8.3 Inject a  1 pil sample of the supernatant
  from the prepared solutions onto the chromat-
  ographic column.  Record the chromatograms
  using the conditions described in Table 1.1.

  9. Calculations
     9.1 Measure the area of the water peak and
  the 2-propanol internal standard peak and mul-
  tiply each area by the appropriate attenuation
   factor to exprev. the peak  areas on  a common
where:                       •» -
/
-------
                                               D 3792

relative at 34 degrees or freedom and the be-   the same operator on different days, should be
tween  laboratory coefficient of variation was   considered suspect if they differ by more than
2.6 % relative at 30 degrees of freedom.  Based   2.9 % relative.
on these coefficients,  the following criteria      10.1.2 Reproducihillty—Two  results,  each
should be used for judging the acceptability of  the mean of duplicate determinations, obtained
results at the 95 * confidence level:             by operators in different laboratories, should
   10.1.1 Repeatability— Two  results, each  the  be considered  suspect  if they differ by more
mean of duplicate determinations, obtained by  than 7.5 % relative.


                        TABLE I  limnmint Paraaitun (Typical C««dHiu«.rt
                           De«aor             thermal conductivity
                           Comma             132 m by U-mm ouuuk di-
                                               amoer packed ««a«0 to 40
                                               mesh porous polymer pack-
                                               «,•
                           Tcnycruura:
                             SumMioki        aOD*C
                             Deiecinr           240*C
                             Cotemi
                                              ITVC
                             CuncrOu        h*tiaa or MUO|«
                               Flow taw        SO mi /mm
                                 rcuntm       IJOmA
                          •* Far ifr*htr*-Tt opcrauo* MI ib* cotasn icmpcnnm at
                         |40*C A/tar we J-f»op«ool ka< dund the cahuna adjud
                         uw  taaacratur* to  170^ oatil DMF dean the ooioma.
                         lUact ike umpcratiM* to l*TC for nbKy>«tn njw.
                                 D3792-4

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                                                 flb
03792
                                                    0.7?
                                          T. «T   O/ffMTTM VL r»A1*r+I-O
                                        FIC.  I


   Tkt American Society ftr Trnatg and Material} later mo potitio* raftering the \tiiday of any potent ngkti oaerted in
etnniaiiiii MI* any item mentioned in ihanandard. Vim oftkitaandardare. ejcfreaiy adnudintt deiermtnario* of ike toUdttt
of any ateJt fattmt rigka, and the ritk of infringement of ate* rrgho, art entirely their otn> i
   TXi ttOHtarl a attjra I* ntimm at my tlm* by lk* nspoiaiUe Ifflutieal nmminer and neat br rr*nr**d e*rrr fn*
•W if net mutd. eMtr nafproud or witkdr***. ftmr rammmts art oivitrj eillurfor rrriiim ofdta standard or for additional
Itmntlardl tni ikauU tit nrfifrmrrf en t TTAf litaaquantn.  four comment; M/? rrcent ctnfttl ci-xsidrroiir* a t mrttinf of the
ii ifatiiMt ttcluueet commiare. *Mrh /ov our fiend. If vaufrei ikat rnr commeiHX lute not rtrriftd a fair Ararm; )vu Mou/J
make your mrwt JriWMt (o (A* X^TW Commmtee on Slandordl. 1*16 R*rr Si.. HulaMpUa. fa. I°I03, »*«•* -ti/ xlMtfuJf a
further bearing regardful yovr comment!, fading taiufoctio* there, yo* mar appeal la llttASTM Board of Director*.
                                             D3792-5

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       Designation: 0 4017-81
       Standard Test Method for

       WATER IN  PAINTS AND  PAINT MATERIALS  BY  KARL
       FISCHER  METHOD1

T^) standard is issued under the fixed designation D 4017; the number immediately following the designation indicates the
-jr of original adoption or. in the case of revision, the year of last revision. A number in parentheses indicates the year of last
•ZZpoiovai. A superscript epsilon (c) indicates an editorial change since the last revision or reapproval.
I. Scope
  1.1  This method is applicable to all paints
i0d paint materials, including resins, mono-
gers, and solvents, with the exception of alde-
hydes and certain active metals, metal oxides
jad metal hydroxides.  While the evaluation
MS limited to ptgmented products containing
unounts of water in the 30 to 70 % range, there
a reason to believe that higher and lower con-
centrations can be determined by this method.

2. Applicable Documents
  11 A STM Standards:
  D1193 Specification for Reagent Water2
  £ 180  Recommended Practice For Devel-
   oping Precision Data on ASTM Methods
   for  Analysis and  Testing  of Industrial
   Chemicals3
  £203  Test  for Water Using Karl Fischer
   Reagent3
  22 Other Document.
  Archer, E E and Jeeter, H. W., Analyst, Vol.
«, 1965, p. 357.

3. Summary of Method
  3.1 The material is dissolved in pyridine, or
mother appropriate solvent, and titrated di-
gctty with standardized Karl Fischer Reagent,
u an electrometric end point. The sluggish
(action with  water in pyridine is accelerated
«it)i  a chemical catalyst, 1-ethylpiperidtne.
  3.2 Pyridine is used as a solvent to minimize
Interference problems caused by ketones. It is
jjso  used because the more commen solvent,
utethanol, will not dissolve many common
,tata and because methanol reacts  with  some
        produce water.
4. Apparatus
  4.1 Karl Fischer Apparatus, manual or auto-
matic, encompassed  by  the description in
Method E 203. Apparatus should be equipped
with a 25-mL buret. Class A, or equivalent.
  4.2 Syringe,  100-y.L capacity, with needle.
  4.3 Syringes, 1-mL and  IQ-mL  capacity,
without needle, but equipped with caps.

5. Reagents
  5.1 Purity  of  Reagents— Reagent  grade
chemicals  shall be used  in all  tests. Unless
otherwise indicated, it is intended that all re-
agents shall conform to the specifications of the
Committee on Analytical Reagents of  the
American Chemical Society, where such spec-
ifications are available.4 Other grades may be
used, provided it is ascertained that the reagent
is of sufficiently high purity to permit its use
without lessening the accuracy of the determi-
nation.
   5.2 Purity of Water— Unless otherwise indi-
cated, references to water shall  be understood
to mean Type II reagent grade water conform-
   1 This method is under the jurisdiction of ASTM Com-
 mittee D-1 on Paint and Related Coatings and Materials and
 is the direct responsibilityof Subcommittee DO 1.21 on Chem-
 ical Analysis of Paint and Paint Materials.
   Current edition approved June 26, 1981. Published Sep-
 tember 1981.
   * Animal Book o] ASTM Standards. Parts 20. 21, 22. 26.
 29. 31.40. and 43.
   a Annual Book of ASTM Standard*. Part 30.
   4 -Reagent Chemicals. American Chemical Society Spec-
 ifications, Am. Chemical Soc., Washington. D. C. For sug-
 gestions on the testing of reagents not listed by the American
 Chemical Society, see "Reagent Chemicals and Standards."
 by Joseph Rosinl D. Van Nostrand Co. Inc.. New York. N
 Y. and the "United States Pharmacopeia."
                                           D4017-1

-------
ing to Specification D 1193.
  5.3 Karl Tocher Reagent *
  5.4 Pyridine, reagent grade.11
  5.5 l-Ethylpiperidine.

6.  Safety Precautions
  6.1 Karl Fischer reagent contains four toxic
compounds, namely iodine, sulfur dioxide, pyr-
idine, and methanol or glycol ether. The  re-
agent should be prepared and dispensed in a
hood. Care must be exercised to avoid inhala-
tion or skin contact. Following accidental con-
tact or spillage, wash with large quantities of
water.
  6.2 Pyridine and methanol solvents should
be treated with the same care as Karl Fischer
reagent.
  6.3 1-ethylpipehdine is of unknown toxicity
and,  therefore, should be  handled with  the
same care as the above materials.
  6.4 Many paint materials are highly  flam-
mable and  should be transferred in  a  well-
ventilated area free from sources of ignition.

7. Procedure
  7.1 Standardization of Karl Fischer Reagent:
   7.1.1  Add enough fresh pyhdine to cover the
electrode tip. plus I  mL of l-ethylpiperidine
catalyst per 20 mL of pyridine. Catalyst per-
forms best at a concentration of about 5 * of
the volume  present
   7.1.2 Fill the 100-^L syringe to about half
full with distilled water and weigh to the nearest
O.i mg.
   7.1.3 Pretitrate the pyridine to the endpoint
indicated by the equipment manufacturer, by
adding just enough  Karl Fischer  Reagent  I
(hereafter referred to as KFR) to cause the  end
point to hold for at least 30 s.
   7.1.3-1  The use of the catalyst greatly in-
creases the reaction  rate between  water  and
 Karl Fischer reagent. To obtain reliable results,
 increase the electrode sensitivity and reduce
 iteration rate to a minimum. Most instruments
 have controls for these functions. Consult in-
structional  manual for  information on these
controls.
   7.1.4 Empty the contents of the syringe  into
 the litrator vessel. Immediately  replace  the
 stopper of the  sample  port and  titrate with
 KFR to the endpoint as described in 7.1.3.
   7.1.5  Repeat standardization until replicate
D4017

values of F agree within I %.  Determine d*
mean of at least two such determinations. Cafff
out calculations  retaining at least one
decimal  figure beyond that of the
data.  Round off figures after final calculation*
  7. 1. 6 Calculation:
                   F'J/P
where:
F -  KFR litre,
J m  water added, g, and
P -  KFR used. mL.
The value for F should be recorded to the fix"
significant digits and should be the mean of*
least two determinations. Typical values are *
the range of 0.004000 to 0.006000 g/mL
  7.2 Analysis of Samples  Waft  More ft*
0.5 % Water.
  7.2. 1 The titration vessel should already coa-
lain pretitrated pyridine  and catalyst, is *•"
scribed in steps 7. 1. 1 and 7. 1. 3 in the standard-
ization procedure. Best results are obtain*
with fresh solvent, that is, contain no previously
titrated specimen in the vessel
  7.2.2 With a l-raL or  10-mL syringe, dn*
 the amount of material indicated in Table I-
   7.2.2. 1 Remove the syringe from the samp*
 pull the plunger out a little further, wipe u*
 excess, material off the syringe, and place » W
 on the syringe tip. Weigh the filled syringe »
 the nearest 0.1 mg.
   /.2.3  Remove the cap. and empty the syr«?
 contenis into the  pretitraied pyridine vessel
 Pull the plunger out and replace the cap. Tin**
 the specimen with  KFR to the  endpoint de-
 scribed in 7.1.3.                          .
   7.2.4  Reweigh the emptied syringe, and <»
 culate the specimen weight by difference.
   7.2.5  Calculation:
 
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                                            flh

  buret and  increase specimen  size as much as
  oeeded. up to 10  g. It should be possible to
  measure moisture  levels  down to   1  ppm
  (0.0001 %)  by this approach (see Note).
   NOTE—Specimens with less than 0.1 % water may
  tequire special handling techniques to prevent pickup
  of atmospheric moisture. The precision of this test
  *as determined with specimens containing higher
  water levels.

 1 Maintenance
   8.1  Cleanup—Clean the titration vessel by
 rinsing with fresh pyridine. Oo not use metha-
 Bol or other solvents.
   8.2  Dryness—Check frequently to  be sure
 that all drying tubes are in good condition and
 tightly connected. Replace dessicant when in-
 dicator color changes through half of the tube.
   8.3 Electrode Performance— If electrode re-
 sponse  is sluggish  or  otherwise off standard,
 take the following steps, in turn, to correct  the
 problem. Test  the electrode  with a titration
 liter each step, to determine if the next step is
 required.
  8.3.1  Wipe  the electrode tip  with a clean
 piper towel.
  8.3.2 Wash the electrode by dipping in con-
 centrated hydrochloric acid for at least 1  min.
 Rinse first with distilled water, then with meth-
 anol.
  8.3.3  Follow manufacturer's instructions on
         D4O17

         resetting endpoint meter.
           8.3.4 Replace power source. See manual for
         replacement procedure.
           8.3.5 Replace the electrode.

         9. Precision
           9.1 The precision estimates are based on an
         in terlaboratory study in which one operator in
         each of seven different laboratories analyzed in
         duplicate, on  two different days, seven samples
         of water-based paints of various types contain-
         ing between 25  to 75 % water. The results were
         analyzed  statistically in accordance with Rec-
         ommended Practice E 180. The within-fabora-
         tories' coefficient of variation was found to be
         t .7 % relative at 98 degrees of freedom, and the
         between-laboratories' coefficient  of variation
         was 5.3 % relative, at  42 degrees of freedom.
         Based on these coefficients,  the following  cri-
         teria should be used forjudging the acceptabil-
         ity of results at the 95 % confidence level.
           9.1.1  Repeatability—Two  results,  each  the
         mean of duplicate determinations, obtained by
         the same operator on different days should be
         considered suspect if they differ by more than
         4.7 %  relative.
           9.1.2  Reproducibility—Tv/o results, each the
         mean of duplicate determinations, obtained by
         operators in  different laboratories  should  be
         considered suspect if they differ by more than
         15.0% relative.
                                  TABLE 1  Specimen Guidelines
                           Expected water.
  Approximate
Specimen Weight.
       g
                              0.5 1.0
                               I 3
                               3 10
                              10-30
                              30-70
                              >70
      5
      25
      I 1

    0.4-1.0
    0.1 0.4
      U.I
Approximate Ti-
iram Volume at
 5 mg/'mL lure.
     mL
     5 10
    10 20
    10 :o
    20 25
    15 25
    20
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                                           D4017-3

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