0-1
February 10, 1973
Revision 0
Sampling Methods and Analytical
Procedures Manual for PCB Disposal
Interim Report
February 10, 1978
PREPARED 3Y: J. Howard Beard, III
John Schaum
Office of Solid Waste
U.S. Environmental
Protection Agency
Washington, D.C. 20460
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PREFACE
This manual is a compendium of sampling methods and
analytical procedures which may be referred to and used by
the ?CB disposal facility owner/operators to assist them
with any sampling and analytical testing which may be required
under 40 CFR Part 761, Polychlorinated Biphenyls. However,
due to the short time period in which this manual was
prepared, the U.S. Environmental Protection Agency is issuing
this manual as an interim document. (The U.S. EPA believes
ehat a sampling methods and analytical procedures manual
has to be available to PCS disposal facility owner/operators
at the time the regulation is finally promulgated to success-
fully implement the site approval process under 40 CFR
Part 761, Polychlorinated Biphenyls.) A final version of
this manual is expected to be issued, after undergoing
further review within the U.S. EPA, by early spring of 1978.
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Table of Contents
i.0 Introduction
1.1 Purpose
1.2 Scope
2.0 Determination of PCB Spill Contamination Levels
3.0 Procedures for Monitoring Feed Rate
3.1 Liquid PCB Wastes
3.2 Solid PC3 Wastes
4.0 Procedures for Monitoring Incineration Operations
and Combustion Products
4.1 Temperature
4.1.1 Temperature Monitoring Locations
4.1.2 Temperature Monitoring Equipment Selection
4.2 Dwell Time
4.3 Scrubber Water Monitoring
4.4 Continuous Stack Monitoring; CO, C02, 02
5.0 Procedures for Conducting and Monitoring A Test B
5.1 Performance
5.2 Combustion Products
5.2.1 CO, C02, 02
5.2.2 HC1
5.2.3 RCL (Total Chlorinated Organic Content) and
PCB (PCB Chemical Substances)
5.2.4 MOX
5.2.5 Total Particulate Matter
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Atachments
Attachment: A
Attachment 3
Attachment C
Attachment D
Attachment E
Attachment F
Attachment G
Tentative Method of Testing for Polychlorinatec
Biphenyls in Spilled Material
Tentative Method of Testing for Polychlorinated
Biphenyls in Water
Determination of CO Emissions from Stationary
Sources
Gas Analysis for C0_, 02/ Excess Air, and
Dry Molecular Weight
Determination of Total Polychlorinated
Biphenyl (PCB) Emissions from Industrial,
Sewage Sludge, and Municipal Refuse Incinerators
(Draft Method)
Determination of Nitrogen Oxide Emissions
from Stationary Sources
Determination of Particulate Emissions
from Stationary Sources
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1.0 INTRODUCTION
i.1 Purpose
The purpose of this manual is to provide guidance to
the PC3 disposal facility owner/operators with any sampling
methods and analytical procedures which may be required
by the Regional Administrator for the parameters specified
in 40 CFR Part 761, Polychlorinated Biphenyls. The manual
provides a procedure for determining the contamination levels
associated with a PCS spill as required under 761.10 (e)
and provides information on incinerator sampling methods
and analytical procedures as required in the "Note" under
761.40.
1.2 Scope
Section 2 of this manual describes the sampling and
analytical procedures for determining the contamination
levels associated with a PC3 spill.
Section 3 describes the procedures for measuring the
flow rare of liquid and non-liquid PC3s fed to the combustion
system. This task is required to be conducted in 40 CFR
761.40(a)(3) of the regulations.
The next section (Section 4) describes the procedures
for monitoring incineration operations and combustion
products. The continuous monitoring of combustion temo-
erature during PCS incineration is required as specified
in 40 CFR, 761.40 (a) ( 4) . Additionally, the continuous
monitoring of CO and C09, and 02 are required during the
incineration of PC3s as prescribed under 40 CFR 761.40(a) (1"
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Dwell time calculations and procedures for sampling ana.
monitoring the scrubber water effluent are also included
within Section 4.
Finally, the procedures for conducting and monitoring
a trial or test burn are included in Section 5. When an
incinerator is first used for the disposal of ?CBs, or when
nodificatons are made that may affect the character of stack
emission products, several parameters must be monitored,
as specified under 40 CFR 761.40 (a) (6) . Additionally, trial
burns may be required of the PCE disposal facility owner/
operator by the Regional Administrator as discussed under
40 CFR 761.40(d)(2).
2.0 DETERMINATION OF PCS SPILL CONTAMINATION LEVEL
The following procedure describes where and how to
sample in the event of a PC3 spill in order to determine
the extent of contamination.
A three dimensional plot of the suspected zone of con-
tamination should first be developed which defines the
perimeter and depth of the suspected area.
The plot should be defined by establishing transects
along the suspected perimeter with sufficient surface samples
taken to define the perimeter. Transects for subsurface
samples should also be established that intersect through
the approximate center of the suspected area with subsurface
samples taken at the perimeter intersection of the transects,
the intersection of the transects at the approximate center
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of the suspected area, and at the approximate center of each
segment formed by the perimeter and the -ranseczs. Figure
1 illustrates the designation of sample locations by use
of transects.
Surface samples should be 500 gram samples taken at
a depth of no greater than 2 millimeters. For suspected
areas greater than 10 square meters, a surface sample point
should consist of four surface samples taken at the corners
of a one meter square grid with the four samples homogenized
to make one composite sample.
Subsurface samples should be removed from the core at
the elevation of interest, i.e., 0.3 meters deep, 0.5 meters
deep, etc. The sample volume should be 100 grain samples
taken at a depth of 0-3 meters or greater. The samples should
then be prepared and analyzed for PCS content using the
air-dried, 10 percent moisture added soxhlet extraction pro-
cedure (see Attachment A). If the analytical results at a
0.3 meter depth are below 500 parts per million PCBs, then
it is presumed that the zone of contamination extends to
0.3 meters for purposes of practical excavation or removal.
If the analytical results exceed 500 parts per million PCBs,
then additional samples must be taken at successive 0.3 meter
levels until the analytical results indicate a concentration
below the 500 parts per million PC3 level. Successive
samples can be avoided by taking a sample at a depth assumed
to be below the zone of contamination. If the concentrati- on
of PCBs is below 500 parts per million, then that samcle
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Figure 1: Designation of Sarnie Locations
Bv Use of Transects
KEY
BBI1
Perirneter of Suspected Area- ABCD
Subsurface Sanples
Perimeter Intersection of the Transects- AA, BE, CC, DD
Intersection of the Transects at the Approximate Center of the
Suspected Area- II
Aproximate Center of Tilach Segment ^cmed by the Perioeter and
the Transects- ABI'ABI', BCT'BCI', CDI'CDI', ADI 'ADI1
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point can be used to define the outer limit of the zone of
contamination. When excavation activities are believed
to be completed, samples should be taken at the excavated
depth to determine if the excavation process has caused
contamination at depths below the originally defined
contaminated zone.
3.0 PROCEDURES FOR MONITORING FEED RATE
3.1 Liquid PCB Wastes
The flow rate of liquids is normally determined by measuring
the pressure drop across an orifice of known size. The pressure
drop is converted to flow rate via fundamental engineering
calculations. However, other devices are more commonly used to
measure the liquid flow such as ones based on mechanically
driven propellors or more advanced instruments based on
magnetic measurements. Such devices are used widely and
available commercially. Information on their installation,
operation, etc., is supplied and should be obtained from the
various vendors. No special consideration for PCB wastes
are necessary compared to other liquids; consequently,
detailed procedures are not specified in this manual.
However, it is recommended that instruments be selected
which provide a continual real-time measurement of the flow-
rate in such a manner that the data can be visually disolaved
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a .-id automatically recorded. It should also be pointec
that the instruments discussed above, whicn measure trie _j-
rate directly, indicate the bulk flow rate of the entire
liquid. If the flow rate of PC3s is needed, it is necessary
to determine the concentration of PC3s in the liquid waste
feed. Sample preparation and analytical procedures for this
purpose are identical to those specified for scrubber
water in Section 4.3 of this manual. The bulk flow rate
is simply multiplied by the percent of ?C3s (by weight) in
the feed to calculate the feed rate of ?C3s.
3 . 2 Solid PCS Wastes
The flow rate of solids is normally determined by weighing
loads and monitoring the time frequency at which these
wastes are fed into the incinerator. Conveyor belts or
other feed mechanisms can be equipped with scales for this
purpose. As with liquid flow measurements, detailed procedures
are not needed for such site specific techniques.
Load weights should be determined by weighing several
representative loads and averaging them. Typically, in
batch operations, the number of loads in a specific time,
such as one hour, are merely counted by the operator.
Sophisticated time frequency measurements are usually not
practical during normal incineration operations. Flow
rates should be calculated and recorded at least several
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As with liquid wastes, if the feed rate of ?C3s is
needed, it is necessary to determine the concentration of
PC3s in the feed material and multiply the % ?C3s by
the bulk feed rate.
4.0 PROCEDURES FOR MONITORING INCINERATION OPERATIONS AND
COMBUSTION PRODUCTS
4.1 Temperature
Temperature should be routinely monitored and recorded
at several locations within the combustion zone of the
chemical waste incinerator, since it is an excellent indicator
of the performance of the combustion process. The choice of
temperature monitoring equipment and its placement or location
within the combustion zone will vary depending on the particular
design of the incinerator. Typically, flame temperature,
afterburner temperature, hot duct temperature, and wall
temperatures are monitored.
Combustion temperature is usually thought of as a value
or range of values which typify the temperature at which
chemical wastes introduced into the combustion chamber are
subjected. Wastes introduced into the combustion zone are
first heated rapidly to the appropriate flame temperature
and then normally cool over time and distance from the flame.
Temperatures within the combustion zones therefore can varv
over a wide range.
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In order to insure that ?C3 v:astes are subjected to
adecua-e -emperature and dwell time conditions, tne rollowinu
specific minimum criteria have been specified in the reg-
ulation (40 CFR Part 761) as combustion criteria:
(1) Maintenance of the introduced ?C3 wastes for a
2-second dwell time at 1200°C (J:100OC) and 3
percent excess oxvgen in the stack gas, or
(2) Maintenance of the introduced ?CB wastes for a
lis-second dwell time at 1600°C (+ 100°C) and 2
percent excess oxygen in the stack gas.
4.1.1 Temperature Monitoring Locations
Compliance with the above criteria can be insured by
maintaining a temperature above the required minimum temp-
erature in the coldest portions of the combustion chamber.
Accordingly, at least one temperature monitor should be
located in this area, which typically is the furthest point
from the flame, such as the point prior to the combustion
zone exit. Specific locational requirements and the number and
type of temperature monitors should be based upon consideration
of particular designs. However, at least two monitors will
normally be required, other than flame temperature monitors,
in order to insure representative monitoring of the combustion
chamber.
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4.1.2 Temperature Monitoring Equipment Selection
Temperature monitoring wi-hin the conibusiton zone
should be performed with thermocouples which are selected
for the appropriate characteristics, in accordance with ~he
composition, size and construction factors. To assist in the
seiec-ion of a proper thermocouple, summary tables and
curves are provided in Tables 1 through 4 and Figures 2 and 3
(see Perry's Chemical Engineers Handbook, 4th Edition, for
a more detailed discussion).
Radiation pyrometers should be used to monitor flame
temperature if the flame is hotter than the practical operating
range of thermocouples. Combustion temperature should
also be monitored by thermocouples shielded from the flame
in order to detect gas temperatures free of hot surface
radiation effects. As specified in the regulation (40
CFR Part 761), the thermocouples should be accurate to
within 100 C of the true temperature.
The thermocouple equipment choice must take into account
maintenance requirements and operating limitations and
should provide a continuous visual display of combustion
temoerature which automaticallv records the data.
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Carmen Types of Thermocouples and Temperature
Ranees in Which Thev Are Used
I.S.A. ; p^riv, ;X,.,-.T.| c,.
'
"
ilt'-
=.;. .-i
T-
•C. | 'f.
c : 00 - p,.,G - =h , f.-^.,.. ._ ! o i,,
P- 87--. Pi-l3<- Kb ' ?'.i::-.-:^: 0 to
A
J, V
T
Ch.-0=!i-P .iU-S.
Iron
Coppir
Ch.-oasl.?
—200 to
'.'on- j— 2CO to
Coo-
df'"
s'.aa-.ac
-200 to
-100 to
Uif
nnr
750
350
1000
T •>
^1
->on
— 300
-:oo
-150
t'ra;'
"C. ' 'F.
K 2650 IJOO 3 'JO
to:OOOH200'i200
to M 0
to 650
100011800
|
600JIIOO
to ISOO|IOCoil800
1
(Perrv's Cnernica.1 Engineers' Handbook,
4th Edition, p. 22-6)
Table 2: Corrosion Characteristics of Cannon
ThernncouDles
Type of
Mnjrn TJ.
Chr
ei-P \
Iron TO, CocstaoUn..
t.nroTTJ?I-P vs. OiajUatan..
InSuencc o: Teaper»turt m
Gu AfmM^l.e •«
P—tsu^c*1 to o'.iiniog itsn
r'.A-.inum corrcxlss tuilv
lOOC'C. .^aould DI» uj*(i IQ
R^-i-in'^ ro ocdiiai
ff-xxl ;o rerj- p-jod
RrfsistAnr* to r-ducing liziorphers:
poor
AJIertad by sulfur, r-ducin; or rji-
furoua EOS, 50:. ud 5TiS
Oxjcino; tad rtcurnt s;moe7ic?res
bar? ii;:.e e^fct on acruracy. £t-Jt
U3sd io dry iC3C"pri-rs»
?. — i'raD'f to cxjd»;t&o: rood u" to
400'C. out pco: ahore 700*C,
R^3L?tiDCT to r»duco; »E3io3phcr«:
rxwi (up to iOO"C. 1
Protect froa OTVHO. c.oiature, sulfur
Subjec; t« oxiJatiou and il:?rvtioQ
iboT*- 400aC. due to copp*r, ^hove
600"C. du* to Coojt»Qtan mre. Coo-
tiaiioati.^a of fopp^r tncaa aJibr*-
lioo sreitly
R.teist3nc* ;o oiidizing
. Re*ist»u« to redurlag »ttn«?h«rt:
sood
Re^uifrt protfcticu from »cid fumes
. Chrosul kltacicei by suL'uroas itir.a*.
pher?
Resistance tn oiidation: good
Rttiftaac- *o reduciaj a:mo3ph«re:
food
s ^e^cal c-ngineers ' Handbook
4th Edition, p.22-7)
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Table 3: Methods of Joining Thermocouple
1*7-1 T-QC?
wires
Planer vs, ;ac::u^ii-.-;i>
Cfiocej.p vs. Alurnci
•-.m-il-!1 -.j. Cotj'j.3Ur.
Ele-.nc-a.-c
hlcciric-drc TC!
;i'irrr •n[c-r
I silver pold,-r
::••'• sol'j::
I "nn»
' Rcrct
! PJMID
(Perry's Chemical Engineers' Handbook,
4th Edition, p.22-7)
Table 4: Reccnmended Maxinrun Operating Temperature o:
Thermocouple Protecting Tubes
— . , . He :j."jr"e '.-.-'. ruj. tin?.
Met*. Tunes
S* am leu at«l
Ca/bon «tpel
Cist iron
U'roueht iroo
1 6 Cr-8 Ni itAialeu stMt. .
28Criro3
Chromel T
Nichrome
20 Cr-32N'i-48 Te aocoloy).-
Inconel -
Ctrsmic TL
Fire clay
SiUimanitc
MulUt«
Silic*
Silicon txfbici^ ... •
550
550
700
700
?iO
MM
1100
MOO
MOO
MCO
1260
()«
1050
1550
1550 !
1530 |
1600 !
1650 i
I JOO
1000
1000
1300
1300
IHW
2000
2000
2000
2000
2000
2300
1900
2300
2200
2600
2900
3COO
(Perry's Chenical Engineers' Handbook,
4th Edition, p.22-7)
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re 2: Temperature-thermal E.M. F Curves for
Cocnxn Tvoes of Thermocouples
70
60
40
1
- 30
LU
10
-10
93 pic1 >ni_^",- C r ~; -''JTI v s 0:31. ~jm
2 £T p'ann^.Ti-!3'"odium vs. piad"-m
3 C.ircmel vs alurel
4 CsDier vs. cons':.itan
5 Iron vs. c"s:c~.'cn
D.C.^rcmef vs co.^.srcntan
i i I i
Reference junction ct 0° C.
I I I I I
-200 0 2CO 4C3 SDO SCO !COO 1200 MOO I€CO
Temperalure , °C.
(Perry's Chemical Engineers' Handbook,
4th Edition, p.22-7)
Lgure 3: Response of Bare Thermocouples' of
Different Size
100
s so
£ 60
40
'\ in siili cir ot 250" F
0 24 6 8 iO
Ti me mm
(Perry's Chemical Engineers' Handbook,
4th Edition, p.22-7)
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4.2 Dwell Time
Dwell time or residence time is the amount: of rime
in which a waste is subjected within the combustion zone
to the combustion temperatures. This time should be estimated
on rhe basis of flow rate calculations.
The least complex calculations for the average dwell time
of combustion gases is equal to the volume of the combustion
chamber divided by the volumetric flow rate of the gas corrected
for temperature and pressure as shown below:
DWELL _ Volume of combustion chamber
TIME Volumetricflow rate ofgas thru chamber
where,
Volumetric flow = Mass flow rate of fuel + Atmospheric
rate of gas mass flow rate of air x Pressure
Density of Air @ T " Combustion
Chamber Pres-
sure
and,
T = Temperature of gases in combustion chamber
(Note: Mass flow rate of fuel includes any combustible
gases derived from the waste.)
Example Calculation
If an ^ncinerator includes a primary combustion chamber of
100 FTJ and an after burn chamber of 2000 FT3, fuel rate =
10,000£/hour, air rate = 90,OOOS/hour> primary chamber
temperature - 3000°F, afterburner temperature = 2500°F,
chamber pressure = 5 psig = 20 psia
Vol Furnace = 100 FT3 + 2000 FT3 = 2lOO FT3 at T = 2500°F
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Volumetric flow rats = 10,000^ - 90,900= X 15 psia
3600 ?ZC X .0134=/FT- X 20 psia
Dwell Time = 2100 = 1.35 5EC
T55I
C-ote: The density of air at various temperatures may be calculated
using the following formula.)
Dens if-- = Ambient Temperature (°K)
13.1 X Combustion Temperature C"X)
or iz rray be obtained from precared tables. Such tables can be found
in the "torrh American Combustion Handbook, North ^nierican Manufacturinq, Inc
The above calculation is a good technique for estimating
residence time; however, the true residence time cannot
be easily calculated on a theoretical basis since the effects
of turbulence are difficult to model. The most accurate
technique for determining dwell time is via actual test
measurements. Such tests can be made by physically introducing
a tracer gas such as radioactive argon into the incinerator
and timing the tracer gas as it passes through the combustion
chamber. The state-of-the-art and expensive equipment asso-
ciated with such tests may make this technique impractical
at most facilities.
4.3 Scrubber Water Monitoring
Scrubber effluent samples should be taken prior to,
during, and after PCS incineration.
Samples of the quench/scrubber water can be taken from
several points depending on the facility design. Listed in
decreasing order of preference for obtaining a composite sample
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are: (I) a holding tank for ponds containing all the scrubber
solution used during a burn, (2) a recirculation cank for
scrubber solutions being recycled, and (3) a pipe through which
these scrubber solutions are being pumped. The advantage
of collecting a sample from holding tanks or ponds is that
iz. is a composite sample and, as such, can be obtained
without the requirement for collecting frequent grab samples
or using automated sampling equipment.
Samples can be collected from valves on tanks or pipes
containing the scrubber solution. If such valves are not
available, a dip tube or sampling bottle device can be dropped
into the tank or pond and allowed to fill. If grab samples
are required to be taken, the facility owner/operator should
mix all samples into a tank or drum. A composite sample
should then be taken as described above. (All sample loc-
ations should be noted for consistency when future samples
are taken.) The scrubber effluent samples should then be
transferred to clean brown bottles equipped with polycetra-
fluoroethylene (PTFE) lined bottle caps and stored in a cool
area.
To prepare the sample for analysis, 1.5 liter alicuots
of the scrubber water samples should be extracted for organics
using the separatory funnel extraction process for oil and arease
from water. This procedure is described in the EPA Handbook
on Methods for Chemical Analyses of Water and Wastes (EPA
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526/6-74-003 MERC, Cincinnati, Ohio 45263). Pentane or
methylene chloride can be substituted for Freon. The extrac-s
should be dried by passing the sample through a 200 x 10.5 mm
glass column containing a 50 mm bed of sodium sulfate which
has been ore-extracted with pentane in a soxhlet for 24 hours.
The extracts should then be concentrated to a 10 milliliter
sample using a Kuderna - Danish concentrating evaporator.
Characterization of the scrubber effluent samples should
also be prepared.
The prepared sample is now ready to be analyzed for
PCS content by gas chromatography-mass spectography. (See
Attachment B.)
4.4 Continuous Stack Monitoring
The PCS marking and disposal regulation (40 CFR
Part 761) requires continuous stack monitoring for CO, CO-,
and 02 . The purpose for these analyses is in part, to insure
99% combustion efficiency, specified as:
Cco9 x 100
Ceo + Cco2
Where Ceo and Cco~ are the concentrations of carbon monoxide
and carbon dioxide, respectively. Additionally, 0-> is
analyzed to insure compliance with excess air requirements.
Carbon monoxide should be continuously measured in the
stack of incinerators while burning PC3s as specified in
CFR 60, Appendix A, Method 10 (Determination of carbon
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monoxide emissions from stationary sources). This method
utilizes a nondispersive infrared (NDIR) analyzer, and is
included in Attachment C of this manual.
Carbon dioxide in the stack should also be continuously
monitored using a NDIR analyzer. The instrument should
be accurate to ^ 1 percent of full scale. A Cco2 concentration
of 0.05 - 5% and 0.02 - 20% is needed. Excess oxygen in
the stack should be continuously monitored using paramagnetic
or electrochemical instrumentation accurate to within +_ 1%
of full scale. A C^ concentration range of 0.05 - 5%,
0.25 - 25% and 1 - 100% are needed.
5. PROCEDURE FOR CONDUCTING AND MONITORING A TEST BURN
5.1 Performance
The test burn should be conducted under conditions
simulating normal operations. All effluent .streams should
be carefully monitored so that the environmental performance
of the incinerator can be evaluated. The test should last
approximately one day, consisting of the following 3 steps:
1) Start-up. The incinerator is fired with fuel
only to purge the system and bring it up to steady-
state at -normal operating conditions.
2) Waste burn. The PCS waste is introduced into
the incinerator at expected normal feed rates.
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The test should only be as long as necessary to
collect sufficient samples for analysis. A four
hour run will probably suffice.
3) Shut-down. Waste feed is terminated and the
incinerator is shut-down per normal procedures.
Prior to the -est burn, PCS waste samples should be
obtained and analyzed for their ?C3 concentrations, bulk
waste feed rates should be determined, and feed rates of
?C3s calculated.
The incinerator should be equipped with all necessary
instruments and controls, as specified in 40 CFR Part 761.
This should include provisions for continuous monitoring
of combustion temperature, feed rates, and CO, CCu and C>2
in the stack. (See Section 4.0 of this manual for more details.)
Additionally, stack sampling equipment for non-continuous
monitoring for specified pollutant concentrations should
be installed and prepared as specified in section 5.2 of
this manual. All instruments should be calibrated.
Prior to start-up, all ash should be removed from
the incinerator and the scrubber system should be purged
and filled with a fresh solution.
As soon as steady-state conditions are reached during
the start-up phase of the test, conditions should be noted
and samples collected to characterize backcround conditions.
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When the monitoring equipment is ready for collecting
the next set of samples, the PCS waste should be introduced
into the incinerator. During the test, samples should
be collected and records kept of the readings of the con-
tinuous monitors. Visual observation of the plume should
also be made.
The following safety procedures should be established
and followed:
Only authorized personnel should be permitted
in the test area during operations.
Waste handling must be performed only by personnel
wearing suitable protective clothing and trained
in handling such materials.
Visual observation of the test system must be
maintained at all times during operation.
Canister gas masks and emergency oxygen resuscitation
units must be available in the immediate test
burn area.
5.2 COMBUSTION PRODUCTS
Non-continuous stack monitoring for CO, C0~, 0-,, KC1,
total particulate matter, NO , total chlorinated organic
A,
content (RCL) and PCS chemical substances, should be conducted
as soecified below.
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CO, CO?, O-i
Stack concentrations of carbon monoxide, carbon
dioxide and oxygen should be determined as specified in
40 C?R 60, EPA Method number 3, which is provided in
Attachment D of this manual.
5.2.2 HC1
Stack concentration for hydrogen chloride should be
determined by collecting -he hydrogen chloride in an
impinger filled with a caustic solution, such as dilute sodium
hydroxide or sodium bicarbonate.
This solution should then be analyzed for chloride
ion concentrations using the mercuric nitrate method. This
method is described in Methods of Air Sampling and Analysis,
2nd Edition, and in Standard Methods for the Examination of
Water and Wastewater. Both are publications of the American
Public Health Association.
5.2.3 RCL and PCBs
Samples for analysis of total chlorinated organic content
(which includes PCBs) should be collected on a solid sorbent
trap, such as XAD-2 Amberlite Resin. Temperature control
must be maintained since the absorptive characteristics
of the trap change with temperature differences. The solid
sorbent trap should be located in the sampling train downstream
from the heated filter and uostream of the first irnsincer.
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The sample is then removed from the solid sorbent trap
via a 24 hour soxhlet extraction with both pentanol and
rnechanol. The extracts should be dried with sodium sulfate
and concentrated to 10 ml. (A more detailed description
of this sampling method is provided in Attachment E.)
Finally, the sample is analyzed for ?C3 and RCL content
by Gas Chromotography-Mass Spectography (see Attachment 3).
5.2.4 NOX
Stack concentrations of nitrogen oxide(s) should be
determined as specified in 40 CFR 60, EPA Method number 7,
which is provided in Attachment F of this manual.
5.2.5 Total Particulate Matter
Mass emission rates of total particulars matter should
be determined as specified in 40 CFR 60, Method 5, which
is provided in Attachment G of this manual.
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REFERENCES
I. Determination of PC3 Spill Contamination Levels,
unpublished report. Available from Hal Snyder,
EPA/Office of Enforcement.
2. EPA Handbook on Methods for Chemical Analyses of Water
and Wastes, EPA publication No. 629/6-74-003, MERC,
Cincinnati, Ohio, 1S74.
5. Standard Methods of Air Sampling and Analysis, 2nd edition,
A?HA, Washington, D.C., 1975.
4. Standard Methods for the Examination of Water and Wastewater,
APHA, Washington, D.C., 1977.
5. Personal, communication. Robert 3. Burns, President,
Industrial Hydronics Corporation, Princeton, N.J., to
J. Howard Beard, III, Office of Solid Waste, U.S. EPA,
January 1978.
6. Personal communication. James Stevens and Joan Berkowitz,
Arthur D. Little, Inc., Cambridge, Massachusetts, to
J. Howard Beard, III, Office of Solid Waste, U.S. EPA,
January, 1978.
7. Personal communication. Carol A. Zee, TRW, Inc.,
Redondo Beach, California, to J. Howard Beard, III,
Office of Solid Waste, U.S. EPA, January, 1978.
8. Analysis of Pesticide Residues in Human and Environmental
Samples, EPA unpublished manuscript prepared by Pesticides
and Toxic Substances Effects Laboratory, National
Environmental Research Center, U.S. EPA, Research Triangle
Park, N.C., 1974.
9. Personal communication. Christopher C. Shih, TRW,
Redondo Beach, California, to J. Howard Beard, III,
Office of Solid Waste, U.S. EPA, January 1978.
10. Destroying Chemical Wastes in Commercial Scale Incinerators,
EPA Contract No. 68-01-2966, Facility Report =6, Office
of Solid Waste, U.S. EPA, Washington, D.C., 1977.
11. Disposal of Organochloride Wastes by Incineration at Sea
(EPA - 430/9-75-014), Washington, D.C., July 1975.
-------
Attachment
Tentative Method of Testing for
Polychlorinated Biphenyls in Spilled Material
-------
Ten-ative Method of Testing for Polychlorinated Biphenyls
(?C3s) in Soilled Material
Any excess liquid is decanted and the sample is spread
in a pyrex dish (8" wide x 12" long x 2" deep). The sample
is air dried at room tempera-cure for about. 4 to 5 days in a
contaminate free area. The dried sample is then ground wich
a procelain mortar and pestle to a uniform particle size.
The sample is then divided by mixing and quartering
until a sub-sample of about 100 grams is obtained (for
surface samples only). The sample is weighed in a 100-ml
beaker. (Add 10—20 % water, seal and thoroughly mix by
tumbling, and equilibrate (minimum 2 hours) prior to extraction,
The extraction is then carried out: in a soxhlet extractor
(see Figure ). Glass wool (about 1 inch deep) is packed
in the bottom of the extraction chamber (40 x 150 mm).
The weighed sample is added and an additional wad of glass wool
is placed on the top. The sample is then extracted using
200 ml of hexane-acetone (9:1) for about 8 hours. The
extraction may be carried out overnight or longer as mav be
necessary for heavily contaminated samples.
The .extract (approximately 200 ml) is then transferred
to a Kuderna-Danish (K-D) evaporator and concentrated to
6 - 10 ml on a warm water bath at approximately 70 C.
(The remainder of the procedure is described in Method 3
(Method for Polychlorinated Biphenyls (?C3s) in Industrial '
Effluents) becinninc with Section 9.4.)
-------
"~~-f- !P^^^f?§^^iS^-': f f ~-~^~-~'^&^^r-e^i'\ •. ^^S^^fd^'f-?^ If^'—SSr'^'t?:
'~^^^^^^^<^'-^^A^^^AS:lf-'-'-'-"~^^^'^r '~J^KJ?' - ^°lpl "'"v-.^^-f^^-j Z^'^^^VJ-^?
,1^1^-C;^-^^;--- -—_-,&-p^^-,.- ._, ^'-<>=i ' - ™';i^_ ^,'-l'^^'?%,.J ~^--'^^^^i1 f i5^-^-_7 ^Ss-t^r^''^ ^^rZ'.^-rrj^'jSl-,"^!
"•rucl-lon of Boilofn Samples
26
-------
9.4 Qualitatively analyse the sample by gas chromatography with an
electron capture detector. From the response obtained decide:
a. If there are any organochlorine pesticides present,
b. If there are any PCB's present,
c. If there is a combination of a and b,
d. If elemental sulfur is present,
e. If the response is too complex to determine a, b, or c.
f. If no response, concentrate to 1.0 ml or less, as required,
according to EPA Method (4), pg. 23 and repeat the analysis
looking for a, b, c, d, and e. Samples containing Aroclors
with a low percentage of chlorine, eg. 1221 and 1232, may
require this concentration in order to achieve the detection
limit of 1 yg/1. Trace quantities of PCB's are often masked
by background which usually occur in the samples.
9.5 If condition _a exists, quantitatively determine the organochiorine
pesticides according to (1].
9.6 If condition b exists, PCS's only are present, no further separation
or cleanup is necessary. Quantitatively determine the PCB's according
to 11.below .
9.7 If condition £ exists, compare peaks obtained from the sample to
those of standard Aroclors and make a judgment as to which Aroclors
may be present. To separate the PCB's from the organochiorine
pesticides, continue as outlined in 10.4.
9.S If condition d_ exists separate the sulfur from the sample using the
method outlined in (10.3) followed by the method in (10.31
9.9 If condition e_ exists then the following macro cleanup and separation
procedures (10.2 and 10.3) should be employed and, if necessarv
followed by the micro separation procedures (10.4 and 10.5).
-------
3-8
LO. Cleanup and Separation Procedures
10.1 Interferences in the fora of distinct peaks and/or high background
in the initial gas chromatographic analysis, as well as, the
physical characteristics of the extract (color, cloudiness,
viscosity) and background knowledge of the sanple will indicate
whether cleanup is required. When these interfere with measure-
ment of the pesticides, or affect column life or detector sen-
sitivity, proceed as directed below.
10.2 Acetonitrile Partition - This procedure is used to remove fats and
oils from the sanrple extracts. It should be noted that not all
pesticides are quantitatively recovered by this procedure. The
analyst must be aware of this and demonstrate the efficiency of
the partitioning for the compounds of interest.
10.2.1 Quantitatively transfer the previously concentrated extract
to a 125 ml separatory funnel with enough hexane to bring
the final volume to 15 ml. Extract.the sample four times
by shaking vigorously for one minute with 50 ml portions
of hexane-saturated acetonitrile.
10.2.2 Combine and transfer the acetonitrile phases to a one-liter
separatory funnel and add 650 ml of distilled water and
40 ml of saturated sodium chloride solution. Mix thor-
oughly for 50-35 seconds. Extract with two 100 ml portions
of hexane by vigorously shaking about 15 seconds.
10.2.3 Combine the hexane extracts in a one-liter separatory funne.
and wash with two 100 ml portions of distilled water. Dis-
card the water layer and pour the hexar.e layer through a
5-4 inch anhvdrous sodiua sulfate colirnn into a 500 ml K-D
-------
3-9
flask equipped with a 10 al ampul. Rinse the separator/
funnel and column with three 10 ml portions of hexane.
10.2.4 Concentrate the extracts to 6-10 ml in the K-D evaporator
in a hot water bath.
10.2.5 Analyze by gas chromatography unless a need for further
cleanup is indicated.
10.3 Florisil Column Adsorption Chromatography
10.3.1 Adjust the sample extract volume to 10 ml.
10.3.2. Place a charge of activated Florisil (weight determined
by lauric-acid value, see Appendix I) in a Chrcmaflex
column. After settling the Florisil by tapping the column
add about one-half inch layer of anhydrous granular sodium
sulfate to the top.
10.3.3 Pre-elute the column, after cooling, with 30-60 ml of
petroleum ether. Discard the eluate and just prior to
exoosure of the sulfate layer to air, quantitatively
transfer the sample extract into the column by decantation
and subsequent petroleum ether washings. Adjust the
elution rate to about 5 ml per minute and, separately,
collect up to three eluates in 500 ml K-D flasks equipped
with 10 ml ampuls. (See Eluate Composition below).
Perform the first elution with 200 ml of 6?6 ethyl ether
in petroleum ether, and the second elution with 200 ml of
15?i ethyl ether in petroleum ether. Perform the third
elution with 200 ml of 50?o ethyl ether - petroleum ether
and the fourth elution with 200 ml of 100% ethvl ether.
-------
5-10
Eluate Composition - By using an equivalent quantity of any
batch of Florisil as determined by its lauric acid value, the
pesticides will be separated into the eluates indicated below:
6% Eluate
Aldrin DDT Pentachlcro-
BHC Heptachlor nitrobenzene
Chlordane Heptachlor EpoxLde Strobane
ODD Lindane Toaaphene
DDE Methoxychlor Trifluralin
Mirex PCB's
15% Eluate 50% Eluate
Endosulfan 1 Endosulfan II
Endrin Cap tan
Dieldrin
Dichloran
Phthalate esters
Certain thiophosphate pesticides will occur in each of the
above fractions as well as the 100% fraction. For additional
information regarding eluate composition, refer to the FDA
Pesticide .Analytical Manual (6).
10.3.4 Concentrate the eluates to 6-10 ml in the K-D evaporator
in a hot water bath.
10.3.3 Analyze fay gas chromatography.
10.4 Silica Gel Micro-Column Separation Procedure (7)
10.4.1 Activation for Silica Gel
10.4.1.1 Place about 20 gm of silica gel in a 100 ml beaker.
Activate at 180 C for approjdmately 16 hours. Transfer
the silica gel to a 100 ml glass stoppered bottle.
When cool, cover with about 55 ml of 0.50% diethyl
ether in ben:ene (volume : volume ). Keep bottle
well sealed. If silica gel collects on the ground
glass surfaces, wash off with the above solvent
-------
3-11
before resealing. Always maintain an excess
of the mixed solvent in bottle (appro-ximately 1/2 in.
above silica gel). Silica gel can be effectively
stored in this manner for several days.
10.4.2 Preparation of the Chromatographic Column
10.4.2.1 Pack the lower 2 mm ID Section of the microcolLmn
with glass wool. Permanently mark the column
120 mm above the glass wool. Using a clean rubber
bulb from a disposable pipet seal the lower end
of the microcolunn. Fill the microcoluzm with
0.50% ether in benzene Cv:v) to the bottom of
the 10/30 joint (Figure 1). Using a disposable
capillary pipet, transfer several aliquots of the
silica gel slurry into the microcolunn. After
approximately 1 cm of silica gel collects in
the bottom of the microcolumn, remove the rubber
bulb seal, tap the column to insure that the
silica gel settles uniformly. Carefully pack
column until the silica gel reaches the 120 ; 2
mm mark. Be sure that there are no air bubbles
in the column. Add about 10 mm of sodium sulfate
to the top of the silica gel. Under low humidity
conditions, the silica gel may coat the sides of
the column and not settle properly. This can be
minimi led by wiping ths outside of the column
with an anti-static solution.
-------
5-12
10.4.2.2 Deactivation of the Silica Gel
a. Fill the microcorumn to the base of
the 10/50 joint with the 0.50% ether-
benzene mixture, assemble reservoir
(using spring clasps) and fill with
approximately 15 ml of the 0.50% ether-
benzene mixture. Attach the air
pressure device (using spring clasps]
and adjust the elution rate to approxi-
mately 1 ml/min. with the air pressure
control. Release the air pressure and
detach reservoir just as the last of
the solvent enters the sodium sulfate.
Fill the column with n-hejcane (not nixed
hexanes) to the base of the 10/50 fitting.
Evaporate all residual benzene from the
reservoir, assemble the reservoir section
and fill with 5 ml of n-hexane. Apply
air pressure and adjust the flow to 1
ml/min. (The n-hejcane flows slightly
faster than the benzene] . Release the air
pressure and remove the reservoir just as
the n-he-xane enters the sodium sulfate.
The column is now ready for use.
b. Pipet a 1.0 ml aliquot of the concentrated
sample extract (previously reduced to a
total volume of 2.0 ml) on to the column.
-------
3-13
As the last of the sample passes into
the sodium sulfate layer, rinse dour.
the internal wall of the column twice
with 0.2S ml of n-hexane. Then assemble
the upper section of the column. As the
last of the n-hexane rinse reaches the
surface of the sodium sulfate, add enough
n-hexane (volume predetermined, see
10.4.3 below) to just elute all of the
PCB's present in the sample. Apply air
pressure and adjust until the flow is
1 ml/min. Collect the desired volume of
eluate (predetermined, see 10.4.3 below)
in an accurately calibrated ampul. .As the
last,of the n-hexane reaches the surface
of the sodium sulfate, release the air
pressure and change the collection ampul.
c. Fill the column with 0.50% diethyl ether
in benzene, again apply air pressure and
adjust flow to 1 ml/min. Collect the
eluate until all of the organochlorine
pesticides of interest have been eluted
(volume predetermined, see 10.4.3 below).
d. .Analyze the eluates by gas chromatograrhy.
10.4.3 Determination of Elution Volumes
10.4.3.1 The elution volumes for the PCB's and the
pesticides depend upon a number of factors which
-------
5-14
are difficult to control. These include
variation in:
a. Mesh si:e of the silica gel
b. Adsorption properties of the silica gel
c. Polar contaminants present in the eluting
solvent
d. Polar materials present in the sample and
sample solvent
e. The dimensions of the microcolumns
Therefore, the optimum elution volume must
be experimentally determined each time a factor
is changed. To determine the elution volumes,
add standard mixtures of Aroclors and pesticides
to the column and serially collect 1 ml elution
volumes. Analyze the individual eluates by gas
chromatography and determine the cut-off volume
for n-hexane and for ether-benzene. Figure 2
shows the retention order of the various PCS
components and of the pesticides. Using this
information, prepare the mixtures required for
calibration of the microcolumn.
10.4.0.2 In determining the volume of hexane required to
elute the PCB's the sample volume (1 ml) and the
volume of n-hexane used to rinse the column wall
must be considered. Thus, if it is determined
that a 10.0 ml elution volume is required to
elute the PCB's, the volume of heaane to be added
-------
5- 15
in addition to the sample voluae but including
the rinse volume should be 9.5 ml.
10.4.5.5 Figure 2 shows that as the average chlorine
content of a PCS mixture decreases the solvent
volume for conrrjlete elution increases. Quali-
tative determination [9.4) indicates which
Aroclors are present and provides the basis
for selection of the ideal elution volume. This
helps to mininiire the quantity of organochlorine
pesticides which will elute along with the low
percent chlorine PCB's and insures the most
efficient separations possible for accurate
analysis.
10.4.5.4 For critical analysis where the PC3's and
pesticides are not separated ccnrpletely, the
column should be accurately calibrated according
to (10.4.5.1) to determine the percent of
material of interest that elutes in each fraction.
Then flush the colunn with an additional 15 nil of
0.50?i ether in benzene followed by 5 ml of n-
hexane and use this reconditioned column for
the sample separation. Using this technique one
can accurately predict the amount ("O of materials
in each micro column fraction.
1C.5 Micro Colunn Separation of Sulfur, PCB's, and Pesticides
10.5.1 See procedure for preparation and packing T.icro colu-m in
?C3 analysis section {1C.4.1 and 1C.-.2).
-------
3-16
10.5.2 Microcolumn Calibration
10.5.2.1 Calibrate the microcolumn for sulfur and
PC3 separation by collecting 1. 0 al fractions
and analysing them by gas chromatography to
determine the following:
1) The fraction with the first elating ?C3's
(.those present in 1260),
2) The fraction with the last eluting PC3' s
(those present in 1221),
3) Tne elution volume for sulfur,
4) The elution volume for the pesticides of
interest in the 0.30% ether-bentene fraction
From these data determine the following:
1) The eluting volume containing only sulfur
(Fraction I).
2) The eluting volume containing the last of
the sulfur and the early eluting PCS's
(Fraction II),
3} The eluting volume containing the remaining
PCB's (Fraction III),
4) The ether-benzene eluting.volume containing
the pesticides of interest (Fraction IV).
10.5.3 Separation Procedure
10.3.3.1 Carefully concentrate the 6% eluate from the
florisil column to 2.0 ml in the graduated
ampul on a warm water bath.
10.5.3.2 Place 1.0 ml (50!s) of the concentrate into
the microcolumn with a 1 ml pipet. Be careful
-------
J-l /
not to get any sulfur crystals into the pipet.
10.5.3.3 Collect Fractions I and II in calibrated centri-
fuge tubes.
Collect Fractions III and IV in calibrated ground
glass stoppered ampules.
10.5.3.4 Sulfur Removal (9) - Add 1 to 2 drops of mercury
to Fraction II stopper and place on a wrist-action
shaker. A black precipitate indicates the presence
of sulfur. After approxiately 20 minutes the
mercury may become entirely reacted or deactivated
by the precipitate. The sample should be quantita-
tively transferred to a clean centrifuge tube and
additional mercury added. When crystals are present-
in the sample, three treatments may be necessary to
remove all the sulfur. .After all the sulfur has
been removed from Fraction II (check using gas
chromatography) combine Fractions II and III.
Adjust the volume to 10 ml and analyze gas chroma-
tography. Be sure no mercury is transferred to
the combined Fractions II and III, since it can
react with certain pesticides.
By combining Fractions II and III, if ?C3's are
present, it is possible to identify the Aroclor(s)
present and a quantitative analysis can be oer-
foraed accordingly. Fraction I can be discarded
since it only contains the bulk of the sulfur.
Analyze Fractions III and IV for the PCB's and
-------
3-18
pesticides. If DDT ana its hoaologs, aldrin,
heptachlor, or technical chlordane are present
along with the PCB's, an additional micro -
column separation can be performed which nay help
to further separate the PCB's from the pesticides
(See 10.4).
11. Quantitative Determination
11.1 Measure the volume of n-hexane eluate, containing the PCB's and
inject 1 to 5 ul into the gas chromatograph. If necessary, adjust
the volume of the eluate to give linear response to the electron
capture detector. The raicrocouloraetric or the electrolytic detector
may be employed to improve specificity for samples having higher
concentrations of PCB's.
11.2 Calculations
11.2.1 When a single Aroclor is present, compare quantitative
Aroclor reference standards (e.g., 1242, 1260) to the un-
known. Measure and sun the areas of the unknown and the
reference Aroclor and calculate the result as follows:
[A] [B] [V ]
Microgram/liter = f(VJ (v }j ~ [N]
A - "g.of Standard Injected
Z of Standard Peak Areas ~ ^j
mm"
•)
B = E of Sample Peak Areas = (ma'1)
V. = Volume of sample injected (yl)
V = Volume of Extract (ul) from which sample
is injected into gas chromatograph
V = Volume of water sarnie e-xtracted (ml)
s
N = 2 when micro column used
1 when micro column not used
-------
3-12
Peak Area = Peak height (an .x Peak Width at
1/2 height
11.2.2 For complex situations, use the calibration method
described below. Small variations in components between
different Aroclor batches make it necessary to obtain
samples of several specific Aroclcrs. These reference
Aroclors can be obtained from Dr. Ronald Webb, Southest
Environmental Research Laboratory, EPA, Athens, Georgia
30601. The procedure is as follows:
11.2.2.1 Using the OV-1 column, chromato graph a known
quantity of each .Aroclor reference standard.
Also chromatograph a sample of p,p'-DDE.
Suggested concentration of each standard is
0.1 ng/ul for the Aroclors and 0.02 ng/ul for
the p,p'-DDE.
11.2.2.2 Determine the relative retention time (KRT} of
each PCS peak in the resulting chroma to grams
using p,p'-DDE as 100. See Figures 3 through 5.
RT x 100
RRT
RTDDE
RRT = Relative Retention Time
RT = Retention tiae of peak of interest
RT
DDE = Retention time of p,p'-DDE
Retention time is measured as that distance in
nm between the first appearance of the solvent
peak and the maximum for the coiroounc.
11.2.2.5 To calibrate the instrument for each PC3
measure the area of each peak.
-------
Area * Peak height CUED) a Peak width at 1/2
height. Using Tables 1 through 6 obtain the
proner mean weight factor, then determine
-?
the response factor ng/nm".
(ng• ) (me_an weight percent)
, : 100
ng/mm = Q—^
ngj_ = ng of Aroclor Standard Injected
Mean weight percent = obtained from Tables 1
through 6.
11.2.2.4 Calculate the RRT value and the area for each
PCB peak in the sample chromatograjn. Compare
the sample chromatogram to those obtained for
each reference Aroclor standard. If it is
apparent that the PC3 peaks present are due to
only one Aroclor then calculate the concentration
of each. PCB using the following formula:
ng PCB = ng/mm .x Area
Where Area = Area (jm ) of sample peak
ng/mm" = Response factor for that peak measured.
Then add the nanograms of PCB's present in the
injection to get the total number of nanograms
of PCB's present. Use the following formula to
calculate the concentration of PCB's in the sacple
In&J JV.J
MicrogranLS/Liter = JTT-T rrrr x INJ
lvsJ lviJ
Vs = volume of water extracted (al)
Vt = volume of extract
-------
3-21
V. = volume of sample injected (j-1)
Ing = SUE of all tits PCB's in nanogranis for
that Aroclor identified
N = 2 when nicrocolunn used
N = 1 when aicrocolunr. not used
The value can then be reported as Micrograns/
Liter PCS's reported as the Aroclor For
samples containing nore than one .-.rocior, use
Figure 9 chronatogras divisional flow chart
to assign a proper response factor to each
peak and also identify the "most likely"
Aroclors present. Calculate the ng of each
PCB isomer present and sun them according
to the divisional flow chart. Using the
forrrula above, calculate the concentration of
the various Arociqrs present in the sairnDle.
12. Reporting Results
12.1 Report results in micrograms per liter without correction for
recovery data. When duplicate and spiked samples are analysed,
all data obtained should be reported.
-------
Table 1
Comoosition of Aroclor 1221 (&)
RRTa
11
14
16
19
21
28
32
[37
[40
Total
Mean
Weight
Percent
31. 8
19.3
10.1
2.8
20.8
5.4
1 .4
1.7
93. 3
Relative
Std. Dev.b
15.8
9.1
9.7
9.7
9.3
13.9
30-1
48.8
Number of
Chlorines0
1
1
2
2
2
2l 85%
3J 15%
2] 101
3j 90%
3
3
aRetention ti^ie relative to p ,p ' -DDE=100 . Measured from
irst appearance of solvent. Overlapping peaks that are
quantitated as one peak are bracketed.
bstandard deviation of seventeen results
of the mean of the results.
CFrorn GC-MS data. Peaks containing mixtures
of different chlorine numbers are bracketed.
as a percentage
of isoners
-------
Table 2
Composition of Aroclor 1232 C8)
RRTa
11
14
16
f20
Ul
28
32
37
40
47
54
58
70
78
Total
Mean
Weight
Percent
16.2
9 .9
7.1
17.8
9.6
3.9
6.8
6.4
4.2
3,4
2.6
4.6
1.7
94.2
Relative
Std. Dev.b
3.4
2.5
6.8
2.4
3. 4
4.7
2.5
2.7
-4.1
3.4
3.7
3.1
7.5
Number of
Chlorines0
1
1
2
2
2
21 40%
3J 60%
3
3
3
4
3] 33%
4J 67%
4
4] 90%
s] 10%
4
aRetention time relative to p ,p'-DDE=100. Measured fron
first appearance of solvent. Overlapping peaks that are
guantitated as one peak are bracketed.
^Standard deviation of four results as a mean of the
results.
CFrom GC-MS data. Peaks containing mixtures of isomers
of different chlorine numbers are bracketed.
-------
Table 3
Composition of Aroclor 1242 C3)
RHT£
11
16
21
28
32
37
40
47
54
58
70
78
84
98
104
125
146
Total
Mean
Weight
Percent
1. 1
2.9
11.3
11.0
6.1
11.5
11.1
8. 8
6 . 8
5.6
10.. 3
3.6
2.7
1.5
2.3
1.6
1.0
98.5
Relative.
Std. Dev.b
35.7
4.2
3.0
5.0
4.7
5.7
6.2
4.3
2.9
3.3
2.8
4.2
9 .7
9.4
16.4
20.4
19 .9
Number of
Chlorines0
1
2
2
21
3J
3
3
3
4
31
4J
4
41
5j
4
5
5
5
51
6J
5
ej
25%
75%
33%
67%
SOI
10%
85%
15%
75%
25%
aRetention time relative to p,p'-DDE=100. Measured from
first appearance of solvent.
bStancard deviation of six results as a cercentaae of
the mean of the results.
C7rom GC-MS data. Peaks containing mixtures of iseiners
of different chlorine numbers are bracketed.
-------
3-25
Table 4
Composition of Aroclor 1248
RRTa
21
28
32
47
40
47
54
58
70
78
84
98
104
112
125
146
Total
Mean
Weight
Percent
1.2
5.2
3.2
8.3
8.3
15.6
9.7
9.3
19.0
6-6
4.9
3.2
3.3
1.2
2.6
1.5
103.1
Relative
Std. Dev.b
23.9
3.3
.3.8
3.6
3.9
1.1
6 .0
5.8
1.4
2-7
2.6
3.2
3.6
6.6
5.9
10. 0
Number of
Chi or
2
3
3
3
31
4j
4
31
4J
4
11
4
5
5
41
5J
5
51
ej
5
6j
ines"
85%
15%
10%
90%
80%
20%
10%
90%
90%
10%
85%
15%
aRetention time relative to p,p'-DDE=100. Measured from
first appearance of solvent.
^Standard deviation of six results as a percentage of
the mean of the results.
cFrom GC-MS data. Peaks containing mixtures of isorrvers
of different chlorine numbers are bracketed.
-------
3-26
Table S
Composition of Aroclor 1254
Mean
RRT£
47
54
58
70
84
98
104
125
146
160
174
203
232
Total
Weight
Percent
6.2
2.9
1.4
13.2
17.3
7.5
13.6
15.0
10. 4
1.3
8.4
1. 8
1.0
100.0
:=::=:::— ^^—— —————— ^-— —
Relative
Std. Dev.b
3.7
2.6
2.8
2.7
1.9
5.3
3.8
2.4
2.7
8.4
5.5
18.6
26.1
Number of
Chi or
4
4
4
41
5J
5
5
5
51
6J
5
6j
6
6
6
7
ines
25%
75%
70%
30%
30%
70%
aRetention time relative to p,p'-DDE=100. Measured frora
first appearance.of solvent.
^Standard deviation of six results as a percentage of the
mean of thfe results.
GFrom GC-MS data. Peaks containing mixtures of iscners
are bracketed.
-------
3-27
Table 6
Composition of Arocior 1260
RRT*
70
84
[~ 98
Li 04
117
125
146
160
174
203
T232
L244
280
332
372
448
523
Total
Mean
Weight
Percent
2.7
4.7
3.8
3.3
12.3
14.1
4.9
12.4
9. 3
9-8
11.0
4.2
4.0
.6
1.5
98.6
Re la
Std.
6.
1.
3.
6 .
3.
3.
2.
2.
4-
3.
2.
5.
8.
25.
10.
tive.
Dev.°
3
6
5
7
3
6
2
7
0
4
4
0
6
3
2
Number of
Chlorines0
5
5
5
6
6
5'
6.
6
6'
7
6
d
60%
40%
1 15%
1 85%
1 50%
J 50%
61 10*
7j 90%
6
7
7
7
8
8
8
e
10%
90%
aRetention time relative to p/p'-DDE=100. Measured from
first appearance of solvent. Overlapping peaks that are
quantitatsd as one peak are bracketed.
^Standard deviation of six results as a mean of the
results.
GFrom GC-MS data. Peaks containing mixtures of isomers
of different chlorine numbers are bracketed.
^Composition determined at the center of peak 104.
Composition determined at the center of peak 232.
-------
COMPRESSED_
AIR
^PRESSURE
^GAUGE
SUPPLY
JXZ
0-5
PSIG
SHUT-OFF
VALVE
REGULATOR
NEEDLE
VALVE
I cm
FLEXIBLE
TUBING
SILICA GEL
5 cm 3
cm
/GLASS
/"WOOL
&
£ 10/30
15 ml
RESERVOIR
1
?
§ 10/30
\2-
23 cm x 4.2 mm 1.0.
2 cm x 2 mm I.D.
FIGURE I. MICROCOLUMN SYSTEM
-------
I SULFUR |
_J
<
h-
o
U-
o
u 20
0
HEPTACHLOR
DDE
M I R E X
ALDRIN
TECHNICAL CHLORODANE
OP' a PP' DDT
X-CHLORDANE
6 8 10
VOLUME n-HEXANE ml
-------
3-30
REFERENCES
(1) "Method for Organochlorine Pesticides in Industrial Effluents," U.S.
Environmental Protection Agency, National Environmental Research Center,
Analytical Quality Control Laboratory, Cincinnati, Ohio 45263, 19"3.
(2) Leoni, V., "The Separation of Fifty Pesticides and Related Compounds
and Polychlorinated Biphenyls into Four Groups by Silica Gel Micro-
column Chromatography," Journal of Chromatographv, 62_, 65 (1971).
(3} McClure, V. E., "Precisely Deactivated Adsorbents Applied to the
Separation of Chlorinated Hydrocarbons " Journal of Chronatographv, 70,
168 (1972). ' ' " —
(4) "Methods for Organic Pesticides in Water and Wastewater," U.S. Environ-
mental Protection Agency, National Environmental Research Center,
Analytical Quality Control Laboratory, Cincinnati, Ohio 45263, 1971.
(3) "Handbook for Analytical Quality Control in Water and Wastewater
Laboratories," Chapter 6, Section 6.4, U.S. Environmental Protection
Agency, National Environmental Research Center, .Analytical Quality
Control Laboratory, Cincinnati, Ohio 4526S, 1972.
(6) "Pesticide Analytical Manual," U.S. Dept. of Health, Education, and
Welfare, Food and Drug Administration, Washington, D.C.
(7) Bellar, T. A. and Lichtenberg, J. J., "Method for the Determination of
Polychlorinated Biphenyls in Water and Sediment," U.S. Environmental
Protection Agency, National Environmental Research Center, .Analytical
Quality Control Laboratory, Cincinnati, Ohio 4526S, 1975.
(8) Webb, R. G. and McCall, A. C. , "Quantitative PCB 'Standards for Electron
Capture Gas Chromatography." Presented at the 164th National ACS
Meeting, New York, August 29, 1972. (Submitted to the Journal of
Chromatographic Science for publication).
(9) Goerlitz, D. F. and Law, L. M., "Note on Removal of Sulfur Interferences
from Sediment- Extracts for Pesticide Analysis," Bulletin of Environmental
Contamination and Toxicology, 6_, 9 (1971).
(10) Mills, P. A., "Variation of Florisil Activity: Sample Method for Measuring
Adsorbent Capacity and its Use in Standardizing Florisil Columns,"
Journal of the Association of Official .Analytical Chemists, 51_, 29 (1963).
(11) Steere, N. V., editor, "Handbook of Laboratory Safety," Chemical Rubber
Company, 18901 Cranwood Parkway, Cleveland, Ohio 4412S, 1971, pp. 230-254.
-------
3-1
APPENDIX I
15. Standardization of Florisil Column by Weight Adjustment Based on Adsorption
of Laurie Acid.
15.1 A rapid method for determining adsorptive capacity of Flcrisii is
based on adsorption of lauric acid from hexane solution (6] (S).
An excess of lauric acid is used and amount not adsorbed is measured
by alkali titration. Weight of lauric acid adsorbed is used to
calculate, by simple proportion, equivalent quantities of Florisil
for batches having different adsorptive capacities.
15.2 Apparatus
15.2.1 Buret. -- 25 ml with 1/10 ml graduations.
15.2.2 Erlenmeyer flasks. — 125 ml narrow mouth and 25 ml, glass
stoppered.
13.2.5 Pipet. -- 10 and 20 ml transfer.
13.2.4 Volumetric flasks. -- 500 ml.
13.3 Reagents and Solvents
15.3.1 Alcohol, ethyl. -- USP or absolute, neutralized to
phenolphthalein.
13.3.2 Hexane. — Distilled from all glass apparatus.
15.3.3 Lauric acid. --Purified, CP.
13.3.4 Lauric acid solution. -- Transfer 10.000 g lauric acid to
500 ml volumetric flask, dissolve in hexane, and dilute to
500 ml (1 ml * 20 mg).
13.3.5 Phenolphthalein Indicator. -- Dissolve 1 g in alcohol and
dilute to 100 ml.
-------
5*2
15.5.6 Sodium hydroxide. -- Dissolve 20 g NaOH (pellets, reagent
gxadej in water and dilute to 500 ml (IN). Dilute 25 ml
IN NaOH to 500 ml with water (0.05NJ. Standardise as follows:
Weigh 100-200 mg lauric acid into 125 ml Erlenmeyer flask.
Add 50 ml neutralized ethyl alcohol and 5 drops phenol-
phthalein indicator; titrate to permanent end point. Calculate
mg lauric acid/ml 0.05 N_ NaOH (about 10 mg/al) .
15.4 Procedure
15.4.1 Transfer 2.000 g Florisil to 25 ml glass stoppered Erienneyer
flasks. Cover loosely with aluminum foil and heat overnight
at 130°C. Stopper, cool to room temperature, add 20.0 ml
lauric acid solution (400 mg), stopper, and shake occasionally
for 15 min. Let adsorbent settle and pipet 10.0 ml of
supernatant into 125 ml Erlenmeyer flask. Avoid inclusion
of any Florisil.
15.4.2 Add 50 ml neutral alcohol and 5 drops indicator solution;
titrate with 0.05N_ to a permanent end point.
15.5 Calculation of Lauric Acid Value and Adjustment of Column Weight
15.5.1 Calculate amount of lauric acid adsorbed on Florisil as
follows:
Lauric Acid value * mg lauric acid/g Florisil = 200 - (ml
required for titration X mg lauric acid/ml 0.05N_NaOH).
15.5.2 To obtain an equivalent quantity of any batch of Florisil,
divide 110 by lauric acid value for that batch and multiply
by 20 g. Verify proper elution of pesticides by 15.6.
-------
0-0
13.6 Test for Proper Elution Pattern and Recovery o£ Pesticides:
Prepare a test mixture containing aidrin, heptachlor epo.xide
p,p'-DDE, dieldrin, Parathion and malathion. Dieldrin and
Parathion should elute in the 15% eluate; all but a trace of
malathion in the 309i eluate and the others in the 6% eluate.
-------
37
AROCLOR 1242
Figure 3. Column: 3% OY-1, Carrier Gas: Nitrogen at 60 ml/min,
Column Temperature: 170 C, Detector: Electron Capture
-------
AROCLOR 1254
I04
125
48
174
232
Figure 4. Column: 3% OY-1, Carrier Gas: Nitrogen at 50 ml/min,
Column Temperature: 170 C, Detector: Electron Capture
-------
AROCLOR 1280
280
528
Figure 5. Column: 3% OY-1, Carrier Gas: Nitrogen at 60 ml/min,
Column Temperature: 170 C, Detector: Electron Capture
-------
/I
AROCLOR 1242
I
I
I
I
0
3
6
21
24
9 12 15 18
RETENTION TIME IN MINUTES
Figure 6. Column: 1.5% OY-17 + 1.95% QF-1, Carrier Gas: Nitrogen
at 60 ml/min, Column Temperature: 200 C, Detector: Electron Capture
-------
AROCLOR 1254
Figuie 7. Column: 1.5% 0V 17 < 1.95%
Detector: Electron Capture.
RETENTION TIME IN MINUTES
OF I, Carrier Gas: Nitrogen at 60 ml/min, Column Temperature: 200 C,
-------
I
I
J_
I
I
I
I
I
I
I
I
I
I
I
I
I
J
54
0
3
12
15
ie
36
39
48
51
21 24 27 30 33
RETENTION TIME IN MINUTES
Figure 8. Column: 1.5% 0V 17 t 1.957. QF-1, Carrier Gas: Nitrogen at 60 ml/min, Column Temperature: 200C, Detector: Election Capture
-------
RRT of first peak < 47?
YES
Is there a distm ct
peak with RRT 78?
RRT
47
58?
YES
NO
YES
Use 1242 for
peaks - RRT 84
Use 1242 for
peaks - RRT 70
Use 1254
for p eaks
- RRT 104
Is there a distinct
peak with RRT 117?
YES
NO
Use 1254 for all
peaksl RRT 174
Use 1260 for
all other peaks
Use 1260 for
all p eaks
Figure 9. Chromatogram Division Flowchart (8)
-------
Attachment B
Tentative Method of Testing for
Polychlorinated Biphenyls in Watei
-------
- o
ENVIRONMENTAL PROTECTION AGENCY
REGIUN II
EDISON. NEW JERSEY O8817
2-SA-T5J OAIL. January 22, 1'J76
••r-CT Tentative Method of Test For
Poiychlcrinntcc] Biphcnyls in Water.
^. -•
Chief,- Technical Support Branch
Tentative Method of Test
For PolychlorinatocI biphcnyls in Water
1. Scope £ Application
1.1 This method covers the determination of certain polychlorinatcd
biphenyls (PCB's) including Aroclors 1016, 1221, 1232, 1242, 1248,
1254 and 1260.
1.2 The method covers the analysis of water samples.
1.3 This method used a Finnigan Mass Spectrometer and Systems Industries
Data System. Other GC/MS systems could be employed for the sair.e
analysis.
2. Applicable References
2.1 0. Hutzinger, S. Safe, V. Zitko, "The Chemistry of PCB's" CRC Press,
Cleveland, Ohio 44128 (1974).
2.2 S. Safe £ 0. Hutnir.ger, "Mass Spectrrraetry of Pesticides and
Pollutants", CRC Press, Cleveland, Ohio, 1973.
2.3 Methods for Organic Pesticides in Water and Wastewntcr, EPA, NERC,
Cincinnati, Ohio 45263, (1971).
2.4 Current Practice in GC-MS Analysis of Orgjiiics in Watur, iil'A
Protection Technoloyy Service, EPA -R2-73-277, August 1973.
2.5 E. J. BonclJ.i, M.S. Sr.ory and J. H. Kjiio'.iL, Dynamic M.i:-. s ^pcc! vm-.v 'try
Vol. 2, 177-202, iieyden & Son Ltd., 1971, U.K.
2.6 E. J. Bonclli, Aii.il . Chc-n. , -\-\, ^03-o^u (1072).
...7 T A. Dellai: S J. J. Licht OIUVM\; , ASTM, ST!% f'7J, "IV-:: 1 '.^ (I')?',).
.--0 J. \v . EichelL.i.'Uu'i." , L. \'.. li.nrj:' .i;u! W. I,. !UuK!e, A:ij_iJ . i.'i r:i. .;.•,
"
-------
-2-
2.9 F. W. McLat'fcrty, "Interpretation c£ Mass Spectra", 2nd Ed., i-.'A
Benjamin, Inc., Reading, Mass., 1973.
3. Summary
PCB's are liquid-liquid extracted and the extract concentrated.
Identification and quantitation is made by computerized gas chromatogra:
mass spectrometry. Either electron impact (70 cv) or chemical ionizatic
(methane reagent gas) mass spectrometry is employed. The detection
limit is approximately 20 ng/1 for the PC3 mixtures listed in Section 1.
when analyzing a 100 ul extract from a one liter water sample and
operating the C.I. mass spectrometer at 1.0 amp filament current, -2200
V continuous dynode, 10~& A/V, 750 microns reagent gas pressure. In
the E.I. mode at 5004" ma, -2200 V., 10~7 A/V, the detection limit is
200 ng/1. At 10~8 A/V, the detection limit is 20 ng/1.
4. Interferences
No interferences are encountered using molecular ion cluster scanning
for biphenyl, mono-, di-, etc. chlorobiphenyls and checking isotope
intensity ratios.
5. Apparatus R Reagents
5.1 Computerized GC/MS.
5.2 Separatory funnel, 2000 ml, with Teflon stopcock.
5.3 100 ml and 2000 ml graduated cylinders.
5.4 Pesticide grade hexane.
5.5 Pesticide grade methylene chloride.
5.6 Pesticide grade acetone-
5.7 Anhydrous sodium sulfatc, granular, reagent grade.
5.8 Sodium chloride, reagent grade.
5.9 Pyrex glass wool.
5.10 Pyrex chromatographic column, approx. 20 mm. o.d., 200 mm lon<;,
with Pyrex glass wool plug at bottom.
5.11 Kuderna-Daniuh (K-U) glassware.
-------
-3-
5.11.1 Synder columns, three-bail (macro).
5.11.2 Evaporative flasks, 500 ml.
5.11.3 Receiver ampuls, 4.0 ml, graduated.
5.11.4 Receiver ampuls, 2.0 ml, graduated to 0.01 ml from 0.30 to
0.00 ml.
5.11.5 Ampul stoppers.
5.11.6 Beaker, 250 ml.
5.12 Microsyringe, 10 ul.
5.13 PC3 mixtures (Aroclor) standards as mentioned in 1.1 above.
6. Extraction of Sample
6.1 Add about 20 gms sodium chloride to a separatory funnel (5.2) .
Transfer about 1 liter of water sample (measured exactly) . Extract
the sample twice with 60 ml of methylcne chloride-hexane (15r- v/v)
and once with 60 ml hexane.
6.2 Dry the combined extracts by passing through a 10 era chromatographic
column (5.8) of anhydrous sodium sulfate (previously rinsed with hexane).
Collect in K-D flask.
6.3 For trace quantities, concentrate to 1.0 ml in 4.0 ml receiver ampul
on steam bath, using dry N2 stream to reach a volume of about 1 ml.
6.4 Transfer extract (rinsing ampul with 1 ml of hexane) to 2.0 ml
ampul and concentrate to 0.10 ml (100 ul) using dry N2 stream. For
larger concentrations of PCD's use a larger volume of extract and/or
operate the M.S. at lower sensitivity to avoid signal saturation.
7. Analysis of Extract by Computerised GC/MS
7.1 Gas chromatocjraphic conditions.
Use 6 ft. X 2 mm i.d. glass column, packed with 3"- Dexsil 300 GC, OV-1
or OV-101 on GO/SO mesh acid-washed Chromosorb G. Helium carrier gas
flow rate of 20 ml/min. inlet, (resulting in about 1.5 ml/min. outlet)
is used. The coJ umn Lcmj>eraturo is proqra::',niL'd fc) 10°C/min. from 150-2tiO°C
(OV-1 coiled coli:i-.ui) on from 175-JSO°C (IVxsil 300 GC U-tubc) . Charge 3 ul
-------
-4-
extract. Allow 75 sec. for solvent to elute. Turn on RF & ionizer i.
start collecting data. Methane (750 u) is the carrier gas for CI MS.
7.2 E.I. Mass Spectrometer Operating Conditions
70 ev. electron energy
-2200 V continuous dynodc
10~7 A/V sensitivity (10~8 A/V if available)
500"1" ua (max) filament current
7.3 E.I. Mass Spectrometer Scan Conditions
Mass Range: 153-157; 188-193; 222-227; 256-261; 290-295; 324-331;
358-364; 392-398.
Integration Time: 50; 50; 50; 50; 50; 50; 50; 50
Samples/AMU: 1; 1; 1; 1; 1; 1; 1; 1
7.4 C.I. MS Operating Conditions
750 microns methane reagent gas (optimize signal on MS by using 652
amu of FC-43 on oscilloscope)
-2200 V continuous dynode
1.0 ma filament current
7.5 C.I. Mass Spectrometer Scan Conditions
Sams as for E.I. (7.3).
8. Qualitative Identification of ?CB's
The presence of PCS mixtures is qualitatively assured from their ma=;s
spectra and GC retention data, using the-molecular ion region for
biphenyl (present in Aroclor 1221 and 1232) and the molecular ion isotr;.
clusters for mono- through heptachloiobiphenyls.
153-157 biphenyl 154M+ (El), 155 (C.I.)
188-193 monochlorobiphenyls
222-227 dichlorobiphenyls
256-261 trichlorobiphenyls
290-296 tetrachlorobiphenyls
324-331 pentachlorobiphenyls
35S-361 hexachlorobiphenyl
392-398 heptachlorobiphenyl
The theoretical peak intensities in these molecular ion regions are
given in Table' A-2, p. 260 of reference 2.9 above. If C.I. (methane)
is used, the masses arc one greater then for E.I,. Identification of
the particular Aroclor mixture or even several mixtures can be
determined by comparison with standards.
-------
-5-
9 . Quantitative Determination o£ PCI3' 3
Once the Aroclor mixture present has been identified (e.g., as Aroclor
1016), a known standard is run and a GC peak present in both (such as
th a:-, largest 013 biphenyl in the case of 101G) is used for quantitation
fro;* total ion intensities in the 256-261 amu region. In the case of
a mixture, such as 1016 and 1254, 1254 is first determined from a Cl^
biphenyl peak not present in 1016. The trichlorobiphenyl peak,
mentioned above, is used to determine the 1016, correcting for the
1254 contribution for that peak. Similar approaches are used for other
mixtures.
A standard is run before and after each daily batch of samples. It has
been found that the total ion intensity over the course of 8 hrs.
varies by about i 5 to 7% from the mean. (2 runs).
10. Minimun Detectable Levels
These are given in the Summary (3).
11. Quality Control Data
In order to assure the validity of the analytical results, samples
of laboratory potable water v/ere measured into 1 liter borosilicatc
bottles closed with aluminum foil-lined screw caps. The water was
then spiked with 1016 Aroclor. The PCB mixture was added as an
acetone solution.
Results
PCB-1016, ug/1
Sample No. Date Added Found
B 8/21 0 <1
L 8/21 5.4 6.4
I 8/21 51.4 53
H 8/21 446 447
H-2 0/26 5.0 6.6
1-2 8/2G yi.2 83 . 5
L-2 8/26 12.M 11.4
Recovery
Per Cent of
Added Amount
119
103
100
112
97
-------
Triplicate samples collected at GIL '.-.'atcr Intake I on 8/26/75
gave the following results:
PCB
Station Date Collected ug/1
Intake I 8/25/75 16
15
15
12. Glassware Preparation
1. All glassware is v/ashed 3 times in an automatic washer,
first with a detergent water solution, then twice with distilled
water and dried.
2. All glassware is then carefully rinsed once with acetone
and once with hcxane.
3. The drying agent, reagent grade granular anhydrous Na-,50^
is dried for a minimum of 24 hours at 105°C. It is kept at this
temperature prior to usage. Only materials used for pesticide and
PCB analyses are kept in this oven.
4. The glass wool and the Na->SO^ are rinsed with hcxane and stored
at 105°C.
Si.
/• ^ Si. - -. (•
- ''^'^^
B. F. Dudenbostel
Chemist
-------
Attachment C
Determination of CO Emissions from
Stationarv Sources
-------
S-i^i5&^i^v»^^J:*c^»^^'^'T*™'^'
vWi»V'",'tf£5*i°i'-? .Vr*#**4p*i~±> »p£5
•iZrSSSiSSSMi-caJ^SefeswtSS
App. A
Title 40—Protection of Environment
METHOD 10—DErmMETATiOfr OF CAJIBON MON-
OXIDE EMISSIONS FROM STATION'AP.T SOUECE3
1. Principle and ApTilica.bilT.ty.
1.1 Pnnc-.pla. An intfrgratad or continuous
gas sample la extra,cvecl from a sampling point
and analyzed for carbon monoxide (CO) con-
tent using a Lull-type noadlsperslva Infra-
red analyser (ND131) or uquivalont.
1J2 Applicability. TbJs method Is appli-
cable lor the determination, of carbon mon-
oxide emissions from stationary sources only
when specmecl by tha test procedures for
determining complla.nce with new source
performance standards. Trie test procedure
will Indicate whether a. continuous or an
Integrated sample U to be used.
2. Range and sensitivity.
2.1 Sengs. 0 to l.OtC1 ppm.
12 Sensitivity. ;'.[[niznu.-n detectable con-
centration la 20 ppm for j, 0 to l.COO ppm
span.
3. InterjererLr.&s. Any substance having a
ntrong absorption of liii'rored energy will
it'-rfere to somo extent. For example, dls-
: Irnlnatlon ratios for water (H_O) and car-
Don dloxlda (CO,) aro 3.5 percent H.O per
7 \ pm CO and 10 pi*_rc;ur. CO. per 10 ppm
CO, respectively, for devices measuring La the
? 500 to 3.000 ppm range. For devices meas-
uring In the 0 to 100 ppin raaco. Interference
ratios can be aa high 3J 3.5 percent H_O per
25 ppm CO and 10 pen:enf CO, per 50 pprn
CO. The use of slllcv. gel anc! ascarlte traps
will ajlevlato the rnsjo" iDterfertrico prob-
lems. The .tncB.-jij-Vi'd gaa I'olumo niuat b« .
corrected u" the3« ti'apa a.re used.
4. Precisian and accT/'ac-:/.
4.1 Precision. The precision of most NDIK
analyzers la approjil'raately ±-,2 percent of
epan.
4.2 .\ccv.racy. The .iccuracy of moot NDER
analyzers Is upproxln.'a.t'-lT i;S percent of
span af:er callbmtlon.
S. Apparatus.
S.I Continuous sample (Figure 10—1).
5.1.1 Probe. Sca.lnjes.3 steel or sheathed
Pyrex ' glass, equipped with ?. CJter to remova
partlculata matter.
5.1.2 Atr-c&oled condenser 01' equivalent.
To remove any excels molitvtre.
SJ2 Inte'jrc.ted sa.-m.pla. ("Fttf-jro 10-2).
5^2.1 Probe. Stainless stefl or sheathed
Pyrei glass, equipped \vtth » filter to remove
partlculate matter.
5.2.2 Air-cooled t.'ondt'-n.Ter or equivalent.
To remove any excels molsci.iro.
6.2.3 Va/rff. Needle va.lv:. or equivalent, to
to adjust now rate.
3J2.-t Pump. Leak-free diaphragm typ«. or
equivalent, to transport gous.
5.2.5 Rate muter. P.otameter. or equivalent,
to measure a flow rungo from 0 to 1.0 liter
per mm. (0.035 cfm).
S.2.6 flexible bay. Tjdlar, or equivalent,
with a capacity of 60 to 90 liters (2 to 3 f t').
LeaJt-t«3t the baj In the laboratory before
using by evacuating b&g with a pump fol-
lowed by a dry gas meter. When evacuation
Is complete, there should be no flow through,
the meter.
5J2.7 Pitot tube. Type S, cr equivalent, at-
tached to the probe so that the sampling
rate can be regulated prcpcrtlonal to the
stack gas velocity when velocity Is varying.
with the time or a sample traverse 13 con-
ducted.
5.3 Analysis (Flg-ure 10-0) .
5 J.I Carbon mononde andy-trr. Nondlsper-
«l7e Infrared spectrometer, or equivalent.
This Instrument should be demonstrated,
preferably by the manufacturer, to meet or
exceed manufacturer's specifications and.
those described In this methcd.
5.3.2 Drying tube. To contain approxi-
mately 200 g of silica gel.
5.3.3 Calibrction gaj. Hefel' to par^Ljrapb.
"6.:.
5.3.4 Filter. As recommended by N
manufacturer.
"Alfl-COOUD CCKSIKStff
'Mention of trade nnme? or specific prod-
ucts cio«s not constitute endorsement by tlau
Environmental Protection Agency.
53.5 CO. removal tube. To contain approxi-
mately 500" g of oscarlte.
63.6 Ice water bath.. For ascarlte and slllcra
gel tubes.
5.3.7 Value. Needle valve, or equivalent, to
adjust flow rate
5.3.8 Rate meter. Rotameter or equivalent
to measure gas flow rate of 0 to 1.0 lltar per
mln. (0.035 cfm) through NTJIR.
5.3.9 Recorder (optional}. To provide per-
manent record of NTJIP. readings.
6. Reagents.
a
8.1 Calibration gas?
of CO In nltrozen (K
prepurt3«i grade of N
tlonai concintritlonj
mately to 80 percent a
span concentration si
the applicable source
The calibration g^se'
the Ennufactnrer to
of the specified concer
6.2 Silica gel. Indict
djrled at 173- C (347' :
63 Ascar-.te. Commg
7. Procedure. - ~
7.1 Siimpliny.
7.1.1 Ccm£tnuo-uj
equipment as siown
sure ail connections
probe In the 3tacS a"
purge the saxnpliig
lyier and be^Ln dra
anaJyzer. .\llow 5 —
to stabUlrc. thea -K
In; as required by '.:
\ ~,3. and 8). CO, con
deterrr-ined by uslns
grated sample prooec
Location
Test
Data _
Op«rator
' Ctoc'
9. Calculatio-n—Ccr
monoxide In the stock
where:
-------
jr.p fol-
..-ua'.icu
•.'.irougb,
eat, at-
i.-r.?ltng
to tie
T~7!r.;
^ con-
--.rated.
-e»t or
pprcxl-
i— apb.
-environmental Protection Agency
App. A
6.1 CzU&ration fa.-;es. E^own concentration
c' CO In nltrogaa (K,) ;or Lasmimenc spaa,
prepuriaed ;jr&as of N, for sero, aad two eddl-
tioaal concentrations corresponding approxi-
mately to 60 percent and 20 percent spa-a_ The
apan concentration s£all not erci?od U times
tne applicable source performance standard.
The calibration gtaes shall bs cerslflod by
tha manufacturer to be within ^2 percent
of the specified coacenrraUoo,
6.2 SiJles gel. Indicating 'type. 6 to 16 mesh,
dried at 175° C (347= P) for 2 hours.
6.3 .-\scctr.te. Coromerciaily available.
7. Procedure.
7.1.1 Continuous sampling. Set up the
equipment is shown In Figure 10-1 mailing
sure all connections are leik "ree. Flacs the
probe lr. the staclt at s sarapllng point imd
purge tto scjapllng lino. Connect the ojia-
lyzer and begin clra?rlng sample Into thet
ar.alyzer. .Vllow 5 minutes lor tns ay3tem
to sr.abUl^a. then record the onalf^er read-
ing as required by the tost procedure. (Sea
t 7.2 and 8). CO] content of ths gas may be
determined by using th8 Method 3 Inta-
gTn.t?d ssunple procedure (38 FR 124883), or
10-1.—Field
by weighing the aacarlto CO, remoTaJ tnb«
aild computing CO, concentration from tha
gaa volvms wunpusd and the weight gain
or the tube.
7.1^2 integrated sampling. Eracruats the
fleilbls bag. Set up the equlpmant aj ihowrx
In Hgvjre 10-2 vrlth the bag disconnect^.
Place tb.8 probe In the stack aad purge the
sampling lino. Connect the bag, making JUT«
that Ell coD-cectloos ara leaJs Iree. Sample att
e, r&ts proporHonsl to the Etaci velodty.
COf coatees ol the ja^ may be determined
by xislng this Method 3 Integrated samplo
proccdurtss (38 KR 248381, or by weighing-
i^he ajicajlte CO. removal tuba and comput-
ing CO3 coaccntratlon ircd the gas voluxna
samplad tuaci tha weight gain ot the tuh«. _
7.2 CO -inaiusl?. Itsscdble tha apparatus aj
shown la Flijuro 10—3, calibrate the Loacru-
mant, s^d perTortn other required
aa descrtlMd In paragraph 8. Purso
with ND prior to introduction ot each
DLreer, tie sample stream through the Instru-
ment for Che teat period, recording the read-
ings. Check; the zero a.nd span again EJ.'ter the
tesc to assure chat any drllt or mail unction
Is detected. Record tha sample data on Table
1O-1.
8. Calibration. Assembls tha apparatus ac-
cording to Figure 10-3. Generally an Instru-
monr requires s warm-up period before sta-
bility Is obtalnad. FolloTu tte manufacturer's
Instructions for spoculc proceilur^i. Ailo-cr a
minimum time of one hour for warm-up.
. During tills tlma check th® sampla condl- _
tlonlng apparatus. I B.. alter, condenser. dry-
Ing tube, and CO, removal tube, to ausure
that ciicci component Is In good opermnlngr
condition. Zero and calibrate tno laatrumont
acoordlricf to tho mucuiacturer'3 procedures
using, respectively, nitrogen and the callbra.
Test - -,-~™.- - .«
Clock tim@
„ , „„ ,„_„_...„ „ Commep.t5:
Rotamctgr setting, liters per minute
(cubic feet per minute)
I
-a'
il'.lca
•t. to
•I'etJt
• per
per-
9. Caicnilat-ion—Concentration of cartxtn monoxide. CaJculat® tha concentration of carbon
moncxlc'o ta tha stacS usLag equation 10—1.
Ccootooh = C'coKDja(l~Fcoj) equatioD 10-1
where:
C
-------
App. A
10. Bibliography.
10.1 McElroy. Fran*. The Intertech NDtB-CO
Analyzer. Presented at lltii Methods
Conference oa Air Pollution, University
of California, Berkeley. Calif, April 1,
1970.
H0.2 Jacobs, M, B., et al.. Continuous Deter-
mination ot Carbon Monoxide- and Hy-
drocarbons In Air by a Modifled Infra-
red Analyzer, J. Air Pollution Control
Association, 3(3): 110-114. August 1959.
Title 40—Protection of Environment
10.3 MSA LIRA Infrared Gas and liquid
Analyzer Instruction Boot, Mine Safety
Appliances Co., Technical Products Di-
vision, Pittsburgh, P».
10.4 Models 21SA, 31SA, and 41SA Infrared
Analyzers, Beckcua Instruments, lac..
Sec&man Instructions 1635-B, Fullsr-
ton, Calif.. October 1367.
10.S Continuous CO Monitoring System.
Model A5511, Interteca Corp.. Princeton,
NJ.
10.8 UNOK Infrared Gas Analyzers, Bendir
Corp., Ronceverte, Weat Virginia.
ADDSNDA
A., ferjorma.net Sptciflcziiona lor ffDIR Carbon Monazide Analyzers.
Rang? (minimum) . O-lOOOppm.
Output (minimum) 0-10mV.
MlaUsiiin datectab'.B sensitivity 20 ppm.
PJsa time, 90 percent (maximum) 30 seconds.
*:I1 time, 90 percent (maximum) 30 seconds. -
2; ro drift (maximum) ._ 10«J in 8 hours.
Sp?,n drift (maximum) 10% in 8 hours.
Precision (minimum) :£ 2% of full scale.
No)-a (maximum) '. :£ 1% of full scale.
Ll.aea.risy (maximum deviation) 2% of fxUl scale.
Interference rejection ratio— ',—': COr—1000 to 1, H:O—500 to 1.
B. Definitions of Performance Speeiftea-
t>'>rw,
• .n'jc—Tie minimum and maximum
BI :i..:arerucnt limits.
Output—Electrical signal which 13 propor-
tional to the measurement; Intended for coa-
incCon to readout or data processing devices.
dually expressed as millivolts or mllllamps
full scale at a given impedance.
Tull scale—The maximum measuring limit
tor a given range.
Minimum detectable itnaiiivity—Tha
smallest amount of input concentration that
can be detected aa tie- concentration ap-
proaches zero.
Accuracy—The degree of agreement .be-
tween a measured value and th» true value;
usually expressed as ± percent of full scale.
Time to 90 percent response—The time in-
terval from a step change In the Input con-
centration at the instrument Inlet to a read-
Ing of 80 percent of the ultimate recorded
concentration.
Rise Time (30 -percent)—Tho Interval be-
tween initial response time &ad time to 90
percent response after a step Increase in the
inlet concentration.
fall Time (SO percent)—The Interval be-
tween Initial response tlrae and time to 90
percent response after a step decrease In the
Inlet concentration.
Zero Drift—The change In Instrument out-
put over a stated time period, utually 24
hours, of unadjusted continuous operation
whoa th» input concentration Is zero; usually
•ipremd u percent full »cal«.
• Span Drift — The change in Iristrument out-
put over a stated time period, usually 24
hours, of unadjusted continuous operailon
when the Input, concentration Is a stated
upscale value; usually expressed as percent
fall scale.
Precision— The degres of agreement be-
tween repeated measurements of the sane
concentration, expressed as the average de-
viation of the single results Iron the ms&n.
A'oiis — Spontaneous deviations from a
mean output not caused by Input concen-
tration changes.
Linearity — The maximum -deviation be-
tween an actual Instrument reading and the
reading predicted by » straight line drawn
between upper and lower calibration points.
MTTHOO 11 — DrrsjujDiATiojf or srnsoGsif strv-
ITDt EMISSIONS FROM STATIONAaT SOU3CT3
1. Principle and. o
1.1 Principle. Hydrogen su!2de (HJS) Is
collected from the source In a series of midget
Iznplngers and reacted with alXallne cad-
mium hydroxide (Cd(OH),] to form cad-
mium sulflde (CdS). The precipitated CdS
is then dissolved in hydrochloric acid and
absorbed- In a Jcnown volume of Iodine solu-
tion. The Iodine consumed Is a measure of
th» H,S content of the gas. Aa implager con-
taining hydrogen peroxide is Included to re-
move SOj as an Interfering species.
U Applicability. This method Is applica-
ble for the determination of hydrogen rul-
flde emissions from stationary sources coly
wh«n specified by the test procedure* for
96
Chapter I-
compliance .
pertortaance standards,'. C'",T.
2. ApparatiiS. '.
2.1 Sampling train. :.•;.-**• ""
2.1.1 Sampling line — 6- to 7-r
Teflon l tubing to connect sara;
sampling valve, with, provision
to prevent condensation; A pr
lag valve prior to ts* Tefloa :
may be required depending'
stream, pressure.
2.12 Impingen — Five rnldgs
each wttix 30-rrU capacity, or eq-
2.1J Ice bath, container — To
sorbiag solution at a constant tt
2.1.4 Silica eel drying tube-
pump and dry gas m»c«r.
2.1 J Needle raise, or equizaie
steel or other corrosion reslstaa
adjust gas flow ri:c.
2.1.8 Pump — Leai fre«, dlapb-
equlvalent, to transport gas, (
If sampling stream under posit:
2.1.7 Dry gas -rr.eter — Su£c!e:
to measure samp:* volume to •
cent.
2.1JS Sate meter — P.otaniater, ;
to measure a Cow rats of 0 tt
minute (0.1 ft'/min).
2.13 Graduated cylinder — 35
2.1.10 Bcrometer — 7o m«»»ure
pressure v/ltMn s^J ^-" (0.1
2.2 Sample P.ecovery.
2^.1 Sample container — SCO-::
pered Iodine Cask.
2.2.2 Pipeite — 50-ml volume t:
2.2.3 Beofcers— 250 tal.
2^.4 Wash hottlf — Class.
2JJ Anctyra.
2.3.1 Flask— iOO-=i glaw-sto:
2.3.2 Burette — O=.s 50 ml.
"2.3.2 Flask — 125-mi coriical.
3. Ssayents. . •- ••- ......
3.1 Sampling.
- 3.1.1 Abiorg-ing solution — Cc
droxloe (Cd(OH>.)— Mis 4J g c
fato hydrate (3 "cdSO,.SH,O) :
sodlura hydroxide (NaOH) 1= 1
tilled water (E.O) . Mis well. .
Note: The cadmium hydrozl;
this mlrtur* will precipitate as
- pension. Therefore, this solut'.
thoroughly mixed before using
even distribution of the cadmiu
3.1— Bydrogen peroxide, 3 per
30 percent hydrogen p*roslde
as needed. Prepare fresh, dallr;
3.2 Ssmple recovery.
3^2.1 Hydrochloric acid soluti
percent by weight — mix 230 =
'Meatiou of trade nimes or s
ucts does uot constitute eudors'
Environmental Protection AgeBw
-------
Attachment
Gas Analysis for C02/ 02/ Excess Air, and
Dry Molecular Weight
-------
4.17BS
-RULES AND REGULATIONS
3. Shirrharv R. T.. W. F. Todd. and W. S. Smith.
Sl^ruliconcfl ot Errors in Stack Sajnplioi Mwmjurameau.
U.i. EaviroixmeiiLa* ProuKUua Araacy, i>*»&rca
Tn*n*la Part, N.C-^PreMQtwl at tb« Annual Mmumot
tn« ALT PoUutioa Coocrol Association, SL Loon, Mo..
Jui» 14-iu. lorn.;
- 4. $ciaf
Vert Joha tVileyuid Sona, lac. UM7.
ft. fluid iUtera — Their Theory und Application,
Amancan 300*17 °f M***fa*-""^J Eocine«o N«w Yon
N.Y. 1WO.
T. A3HRAE Hindboot of Fur*iamtauli 1077, p. 2S.
ft AAnnai 3oa* o/ AiTM Standards, Part 2L ly'-L p,
W V.
•). VoUaro. R, F. Oojd*Un« for Tyr» 3 Pilot Tub*
CoDorouon. C.S. EnnronmftntaJ Protection Agency.
Kee*A.-cb TiAn*tficaenL C 3. Envtrorunaatol rroiectloa \««TICT.
ZrnJsioa Measure mem Brincti, R*>wj-cn Tnan^U
Parr, N.C. October lOTti.
11 VoUaro. P.. F. EstAhlrstunwt oJ * Sueliru Co«ffl-
citnt Vslua (r>r properly Conjtruct*d Typ* ^ HI tot
Tuoea. U.S. Enrirorunsntal ProtcruoQ Air 1976,
11 VoUaro, R. F Ao Er&luAtlon of Siaglfl-V*locily
CabTpraoon Techniqaes aj a Mania of Det&nmnlug Typo
8 Phot Tut* Co«ffic:enti. C.3. EnTirooroftauil Protrt>
M"" A^dncy. Eaission Men5ur^tD«Qt Branch, R«Aafcii
Tnar.el« Part. N.C. Amrujt 1975.
It Vollaro. R. F. The L"» of Typ« S PItot Tub« toe
the Measurrment of Low Velocities, O'.S. EnviroameotaJ
Protect! OQ Agency, EmissioD Mw^suremftot Bnuica,
«Jch Tnanji^'Parfe. N.C. Nov«mb«r 19 T6.
SmiLh, Marvin L. Velocity CaJibranon of EPA
Sourc* SompUnz Prot>e. Coited Technologies
Corporauon, Pratt and Whicooy Aircraft
East Hanlord COOTL 1371. -
16. Vollaro. R. F. Rtcarm: ended Procwia
TT^versea LD DTICLS sanller than 12 Inches in Diametw.
U.S. E D TITD OIE e n tiU Protect too Agency, Eoussroti
N'ea^ojBmeni Branch. P.esoArcii Tnangia P*ft, N.C.
NoTBtnb« 197TI.
17. Over. z. and R, C. PaakbnrK- The
of AiJ Flow. ^Lh Ed_, London. Penramon Press. 1
13. VoUart>, B- F. A survey oi CornrnerclaUy Av
Prob**, PrepfLred by c
MIOULTT o.' Ui« EQTir
ni"s. U.S. Es'Tr?cn2eQLaJ Prorectlon Aeencv,
it«iscj-?aa*tic Branch. Res^arcfi TrlangL*
.
^ "*'- C- C. S\. Pierre, D. S. StnjLh. D.
. &MUMT. Ai Ejp*nm«aL4J
UoIvenitT o^ Wtndjw for tit
msnt, Toroaw,
3 - OjJ X**AJ.T3» rOB
l.l Prlnrlpla. A cu y
by on«» of ii>* following
U ul
Crora »
r OercBUt carbon dloEd« (COu, p»irceJit ciy-
Cea iO:>. and. i/ necRtsary. rrotnt o»rcM>n c3oaoi_!d«
(CO). U B dry mowcuiw weig.it ddUfnircaUoa Li to b*
cxftda, p4Lh«ir in ur»t or ft FTTHO ' aaaJ> ter 01*7 b« awd
far tb« anjJysLJ: (or imress *ir or cnxuAioo nc* correcuoa
factor drUrnunuLioa. *n Orso-i wiaivter tnujt N* ir«t*d.
IJ2 App.icabuKj-. Ttuj mecaod is ayplic^bl* lor d*-
tcrmioJns COi ind Oi coacejatnLioas, »ic«» MT, ami
dry mouictiJjLr "Mffbt of ft wmipl« Lmm a s&j scrnaon o^ a
loull-ioeJ corobuJUoQ procwa,
topUcuiDU looi-ntr -TTXAUM vh<
inat compountlj och«r U^MI COi. Oi. CO, and -
(Nt) ire uot prasent la coact ntnuioTn jmaa«uU u>
(jcnfr meiiio«l3. 04 wall xi niodiflcucionj Uy Lh* prtx»-
dur» described hartin, ar* a no appbcauu for irrcJ? or \J
of cb« »oov9 - J « c< rnLLoa d o nj . EtamD'** of sp#-nXio ouO-
odj and aiodliiisiuoaj mcluo«. 1 1) a miua-rxwnt. ^*cnp*
Un< en i* i bod asan to Oni»L anjjJyier io »raUTTc tndl-
vidaaJ ^rxb samplrt ootaaawi at c_j*^i r
temj described ber*ia. oubcr iimpboz jy^Kerru (c.t-
, liquid displiictmeni) m^y b« ui«*d pro»id&d sucn 57*1*033
a/« capabl* of obtainun? a rspreieQCiUvu 5ajno<« wid
nmintainmj a coruujiL sampunsf rate, and are OLQtrwTa*
capaiils ^of yieJdia? iccspt-ibla rasulLi. L's* of sucn
Tysiemsla yublwt LO ttio approrii of tbe Ad-miTLUUTiLor.
i.1 Grai) SajnoLuiij r Fiyxira 3-1).
2-1.1 ProtM. The prob« sooold b* rasda of yta-olesm
nael or boronit\cn.Le pLa^s lubuix and sbotud b-» «gmpp*d
wnb an m-itaci or om -a Lac It fuuer LO rBmor^ pan.cui*u>
raaLLar (i piu^ of glass wool is saujfuctory lor LQU our-
' po»). Aoy other ciflLeriAi iaen LO Oi, COi, CO. and Ni
and re^utant to tomFwracuj-B at iArnpiuut condiuoru may
b« used for the probe; ammpios o/ ruch
aJurojnuia. copper, qaaru gbiiJ and Tflilon.
J.I.- Pump^ A orse-way 5Cjue«i9 oulb, &f eq
b used io imcLspon -.ha £us saxapis io the
2.2 lnte
-------
RULES AND REGULATIONS
PROBE
FLEXIBLE TUBING
FILTER (GLASS WOOL)
SQUEEZEBULS
•TO ANALYSER
Figure 3-1. Grab-sampling train.
RATE METER
AIR-COOLED
CONDENSER
PROBE
\
FILTER
(GLASS WOOL)
VALVE
QUICK DISCONNECT *-Tj
: W.
RIGID CONTAINER'
BAG
Figure 3-2. Integrated gas-sampling train.
KOERAJ. JtWISTU, VOL. 42, NO. 160—THURSDAY, AUGUST 18, 1977
-------
41770
RULES AND REGULATIONS
2.2.2 Condenser. An air-cooled or water-cooled eoo-
donser. or other condenser tnai will aoc rrmOTa Ow
COi, CO. and Ni. may be used to retno»« eiees matenn
which would tatafcn with UM operacua ol tae pump
tad flow meur. — ••-.•
2.2.3 Valre. A aexila T«in Is eod to adjust 3»tnpt»
pu flaw ra(«. ' • —
2.2.4 PTIIBB. A v»*-« pump. «
tquiTalwu. Is us*d to transport sample «»u u> in« flexible
bat. IruLAU a small snnte unk b*r»een tn» pump and
ran :net*r to «iirainate CM oul»Uon eJltnl ol to* di*-
phrmrni pump on the rotarneur.
:.2J Kau Meter. TH« rotaaeur. or eqolretant rate
neter. nwd ihould be raoaoie ol measuring Jo" nit*
u> within 3:2 o«e«ni of ire j»l««t«d iH» rat*. A low
raw ran»» or JOO to HHMan'/min is jiii^rsi«i.
2.2.8 FlttibU Da*. .Ml? lea*-lr«» pi»J"c " z.. Tfdiar.
Mylar. Teflon) or piasuc-coaKd aluminum '•?•!.. alumi-
num Mylar) bat:. or •wiuirnient. ha^iru > capacity
p>-,;:junt with, the selected flow rate and time Icnjtn
ol t.ie lot ran. may be osKl. A capacity in <°« ""»!• °<
U w •» uten Is surctsud.
To leak-cheek the oac. connect It to i water manometer
ind prwnmif the o« 10 J to 10 eta K:O ''.• to 4 la. ErO).
AJUrw to st»n* dry molKular
tadjcaud ui o«ctloo A i.
3.2A R*p"«i UM anaiytiA and calculadQn procadtina
cnUJ tb* uidinduai dry molecular wwc&u for &ny t^r««
analyau diller (roui loetr tnaan by oo caor* Uiaa OJ
Z.'1-moie (OJ IbAb-moUl. Ann<« theae UXTM coUcubw
weittbu. and rapon Uio ranilU to Ux ncanm 0.1 ti-ox»«
(0.1 IbiltxaoU).
3.3 Multi-Point. IntefraUd SampUof aod Aoalytxal
Prwudun.
3J.1 Oolwi othanrtM rwciUed by tb« Adalnl>
traxor, a DUnimam of «ltbt tr«v«r9* pointi isiu >t uvd
for clroular slack* bannf diamcun leo tb«o 0.61 in
(14 tn.). a mmrmum o( nine sbaU be 03*^1 for rectACjralar
nacka harms, tqamltat dlaaeun \a* U:an O.S1 a
(24 in.), and a nmitaum of twelve cravtne poinu 3ball
be cuvd (or all otbtr c«Ma..Tbe tnvarM poinu snail &•
located acoordinc to Method 1. .Thr tue of fewer POLCLI
U mb)eet to approval ol tbe AdaunlJBUtor.
3.3.2 Follow th« priccdnrae cxiuined In Sec do as 3J12
through 3JJ, ticrpt >'nr the loUovnnc tranne all mat-
pUog poinu and saiapU at *acn point (or an equal lea^tJl
o( tiiaa. Record umpUn| data ai jnown la Fijian 3-i.
Ran CarrniJM fnOtr or Ezcttt .\tr
NOTC.— A 7yriu-trP* oomborooo m analyiar la not
arrnririi-U* lor urm u or eoiuaoa rau corr*cuon bcior
^^JT^jp^^i^miliae aopravtd by tba Administrator.
II t>ot& percent COi anti p«rr«ot Oi are aaeaatirad. tbe
aoaiyueal remlu of any oi the tbrm prtrmlorm
beio-w nsay auo b* osed i
£»ch of the three pnxadara b«low ^ball b« aand only
whfn vp^tiijifd in an applicable wbpart u/ th* standard!.
Tbe OM of tbwe procetrunw for otner purp«M>« tnuil b**e
rpeeuta pnor aoproTul of toe Adniiaiatnior.
4.1 ai04le>i'ouu. Grab SampUAf ami AnalyUcal
4.1.1 The mmpllnt point tn the dact ihaJl tfthir CM
at the eanrrotd of tne cruen^fcuon or at a point DO eloaer
utnewaiUtt-.^r. 100m uufu.onleaiauierwuxpeculeil
by the Adau:iutr%uur.
4.1^ 3«t up tbe equipment M ihovrn In Fliun 3-1,
^•'^irt sure all ooonectionj abaail o< tne anjuyier are
l^bt aod KMl-trr*. L>*eJ«nKK tne Orau aoalrur *a-
oorrluK to Ue proetdur* de»enb«l la 3*oioa V. Ttuj
tr»yi ^i-c.
u. For Oral mi Fyrita ir JT"» rnaln-
u opuration proc«du;-t». taUo» t j« instnicQooj
«comm«nd«l by th» cifloulJctnrw, Uilaa olbertnai
srv«'iflet». ia» meajunm burttt* o«
' tin O.tot muK t»«\ »: i^ast 0,1 paroent
Asy <•' *.t» tnr« sampta« »n« b»
H tb< fcntroiU o/ -Jw CTWJ section or i: » point no eJo**
to tilt "nUa ^s»a 1.00 m J 5.3 ft ). unUaa otbenru* ip»di*l
t> aun. _
1.2 6*t up tt* »qalr=<«B M lixnrn in r*tnr»
lojif sure ill coimcj-303 »h««d by
followinj tbe procedure ia Section 4: hoireYW. Uu> leak-
check Is optional.
3 1J Place t--.e probe in the stack, wittt tbe Sp al tha
probe poji'.iooed al Ue sampling point; purge the sasipt-
ins UneT Draw a sample into :b« anAlyter and Imme-
diately analyr« l« <°r P«reect COi and percent Oa, Deur-
mine Uw percentage oi the gas Out u Ni and CO by
subtract!:,* the sum of tbe percent COi and p*rcan: O»
torn 100 percent. Calculate Use dry molecular wej*ht aa
Indicated in Section 8.3.
3.1.4 R«p«: tbe samplias, analysis, and calculation
procedures, ur.til the dry moiecular i-eijats of any three
crab samples difltr frora tlwr mean by no more than
0 3 iVs-tnoie (0.3 Ui/lu-mc4*). Average these three molec-
ular weijh'j. an-; r-port tha results to the nearest
01 t/z-mole (Ih/lb-r-.ole). . . , ,
3.2 Sinfle-Point.lnietrated Sampling and Analytical
S.l; "rhe sampling poll' ta the duct shall be located
"IsS^tcakihuck (op'tTonal) the fleiible ba? as In
Section 2i«. Set up ihu equipment as shown in '-jure
3-2. Just prior to sampling. leak-check (.optional) the
trtla by pLtcins a Yar.uu.-J cauee at the condensw ir.let,
pullinit » Yuc'jum ol at least JM mm Hz (10 La. Hg),
plugging tbe outlet at the quick iiscor.nect, and then
turnins ol the pan?. Tbe taciturn, should romam stable
for alienator nunuu. Eracua'.c tbe£e.tibU: bag. Conn«t
the prnb- and place it in the stiC*. with tbe tip ol the
probe poj'.uoncd at tfte sampling pntnr purie the samp>-
irj Ui.e. X*it. cof.r.-ct the bi? and calM sure that all
connections are ti!'i: und l<^lc te«-
323 Sample »•. 4 constant rale. Tbe samBUrjt run
soould be simiUianteus with, and for the same total
>r,etb of ti:n° u. the pollutant emission rate determina-
tion. Coilo. '.-..-.n of at l<-ast 30 Uten (1.00 ft') of sample cas
is rtcorv.n: -v.JjU: hownYer, smaller Yolume* may be
coll'-.'Ud. ;f desired.
3.2.4 Obtain one Integrated Rue gas sample anrlnc
eacb pullutant e;ni5-ion rite dciermitiation. Within 3
h'nin afur tae simple is inktn. aiialyte it lor percent
Cf)i ind rwrcfnt 0; uSitiB citm-r an Orsat anilytcr or a
Fyrite-type comtristiun gas analyzer. If an Orsat ana-
lyser 15 used, it is recommenced that th* Orsat U-ik-
i-~-t rt»!u-ribed In Section i be fwrfi-rmi-d l>»!'»re this
Oftcrmuuuon: howeYer. th? rhiv k i; optional. Deter-
t£iDeth» r^rcrnxjp of the zas that \- N':ar-l CL>by suS
U*.iing tlie sum of the percent CO »:.u percent Oi
TIME
TRAVERSE
FT.
AVERAGE
% 0 E V "* " 1 •a^aw^.nwaw^ne. ) 1 HQ /
\ n awn / *
Q
1pm
MUST BE < 1*0%
%DEV.a
Figure 3-3. Sampling rate data.
4.1 J P'.oc* the probe In tbe i tack, with the tip of th»
probe poallloned at tbe sampling point: ptme toe sao-
ruin^ Uoe. Draw a sample Into tbe analyzer, for emission
rate correction factor determination, immediately ana>.
lyre tbe sample, as outlined m Sections 4.1.4 acd 4.U.
for percent COt or percent Ox, If eicess clr Is desired,
proceed as follows: (1) immediately acajyte the sample.
as la Sections 4.1.4 and 4-l.i. for percent CO;, Oi. ar.d
CO: (2) determine the percentage of the ms that Is Ni
by subtracting tbe sum. of the percent COi, percent Ot.
and percent CO from 100 percent: and (.:> calculate
percent eicen air as outlined in Section i.2.
4.1.4 To ensure complete abaorprJon ol tbe CO-. O-.
or IX applicable. CO, make repealed passes through each
absorbing solution ontil two consecutive msdio^s are
the same. SeYcral passes (three or (oorl should b» =ade
between readings. (If constant readings cannot be
obtained after tuc.e cocoecuttYe r»iJ2{3, replies the
absorbing solutlim.)
4J.S After tbe analysis Is completea, leak-cheer
(mandatory) the Orsat analyzer once ajain. as ducribtd
In Section 3. For the results of tbe analysis to be ralid.
the Orut acalyter must pass this leak test before and
after tbe analysis. NOTE.—Since thU sinil*-poisl. ?rab
sampling and analytical procedure is normally conduct**!
In conjunction with a single-point, grub sampiiag »ad
analytical procedure (or a pollutant, only one anaiyrts
is ordinarily conducted. Therefore, yreat cart nsust w
taken to obtain a Yalid sample and analysis. Although
In most cases only COi or Oi is requind. it is recom-
mended that both COi and O: be measured, and teat
Citation J in tbe Bibliography be used to Yalidau the
analytical data.
4.S Sinslo-hoint, Intejrated Samplinj and Aaslr:I»l
Trocedurp.
4.2.1 The sampling point ia the duct shall oe loca:^4
as specified in Section 4.1.1.
4.J/J Lenk-chrck (mandatory) the fi»t:b!» ba»_as 13
Seciion 2.'J.«. S'"t up llie e'iui|im*nt as sho'*^. .^ 7;?ir*
' U
the coa-1-rti^r ir.lr'..
im Hg (10 J. Uti.
filugj;ng tte cutlet it the quick disco&aect, isi ^«a
beciion :...». S'"t up me e'luipmem u
3-2. Just prior to s^inplinc. le:vii-chec«
tnin by pLacinc a Y^'imn: cau?K at t!n
pullinj a YKuun of n'. least i*> rim
' tcrclag oC the pomp. The. ncrona shaQ remain (table
for at '.east O.S minnu. E-ramta toe UailbU be*. Coo-
nect tbe probe and place i: in t.Vstsck, mthlhe Upof the
probe positioned al the sampuru point: puro the sam-
pling Una. Next, connect the bag aod make sera thai
all connections are tijrht and leak free,
4.2.3 Sample at a constant rate, or u spectCed by tbe
Administrator. Tbe sampling run must be simultaneous
imh. and lor the same total length of time as. the pollut-
ant rmialon rate determination. Collect at laait 30
liters il.OO ft') of sample gas. Smaller Yolumes may be
collected, subject to approval of the Adminisinuor.
4.2.4 Obtain one intrgrated iue gas sample during
each pollutant emission rate determination. For emission
r*-* crrr*cuon tsc'-or determination, analyze the sample
Tl-.hia 4 hours ahrr U is taken for percent COtor percent
Oi (u outlined ia Sections 4.2J throuj* 4.1.7). The
Orsat-analyzer mnst be leak-checked (?re Section o)
br'ivre the analysis. U excess air is d6*ir>?d. proceed as
follows: (1) »-ithin 4 hours alter the sejnple Is taken.
aaalyie it (as in Sections 4.2-S through 4.2,7) tor percent
COi Ot and CO: (2) dttensiine ;he peroatage of tbe
fasttatisNibysubtractru thesumotths percent COt
p^wtt O-. asd p»rwut CO fr?m 100 percent; (3) c»l-
cu!»:e prcent ?i:ess air. as outlined ia oevtion 6.2.
4.2.J To ensu-'» complete absorption of tbe COt. Oi.
er if appucable. CO, make repeated passes through eacn
a^.-fj: ticg solution unril two sonsvcntiYe r-*djcjs are tbe
Sims, i-r-ral passes itliree cr four) sbouiu be made be-
•.•"-n readings. (If cocstant roadlnfs canaot be obtiinsd
iT:.* Repeat the analysis tmtll the foUowlng criteria
ar- met:
4.2.-LI For percent COi, rep«»t the a.^aljtlcal pro-
c»T— *• ur.ttl the results of any three analyses diiler by no
n;:r» '~.IQ :aj 0.3 percent by volume »b*n COi o grantee
u.3-' 4. • r^rrer.t or ''b) 0.2 ^TH0 ci^cr by oo more
H-D5RAI REC1STEX, VOl. 42, NO. 16*—THURSDAY, AUGUST 13, 1777
-------
RULES AND REGULATIONS
7nlum» \shen C^ is less th%o l.! 0
iic 5v Tolujoe 'I'beQ Or is srwiLtr
ui- Ltia Uirw seccpUb/*
ih.d resuJu LO tO«
pwiTfi.i. ^r -, i 0._' ^'
Ulan ! i.O f-T- out. A^
~rcent O; aad ropori, ih.
portent.
<_2.6.3 For pcrwnt CO,
cTart imtil LQ« IT5U1L3 oi dny tfinre a.ix»l 73 ITS i3 corr.plft
i-n-tndiiorv! tb« Orssc aoaJ y-r«r one- araiQ. as dftsribM
n o. Forihe rcsuiu cf the n;aJ \-sis to oe vajict. : !-.e
ai^ier must na^a tbis le4t l«ii o*»(or« aad al^r
jj. Note AKhuunb 01 moal L'^iar.Cf^ onJ v COj
or O] 13 requ^rxi, i: 13 reco nun ended, iiiat both CO? ind
Oi be rrun-iircd. ind that Clcauon i m ;b# DiDUo^rmpay
bt u:«l 10 TiucL»t* ihe anjJyxjoU daii.
•1 3 .Maiu-tPomt, I.iic^raLeU 3*icpun? and Analytical
procouir?.
4.0,1 IjcLh tbe minimam nambier
U:
3.1.1 3nni the liquid levpt m e^cb pip*ct« up to th«
re/i-reccB LQATI on Ui« eapdiary njbia^ and. then clos« tti«
pipene uiopcocfc.
0.1.2 Kaii* the l*T<>liQg bulb Tufflaentl> fo bnnz the
cor-laiDa ligojJ m^p-^coa onco tne rrwJusied portiou o(
Uj« bureue and t.Vn da-ie ibe maoaioJd jiopcoc
5.1.3 Ri^c-Trd tbfl meaisciLJ posiuoa.
5.1.4 Obser79
liquid l«v«J la tb
nuontes.
5.U For the Or?At analyirr to pa^s tbe leak-ch*dE,
two conc!i;(on3auyi b* met.
.S.i.5,1 Th«t Uqold >T«1 in *acb pip«tte must not fall
belov t&o bociom o/ Uw capillary uaDing danoj tois
+-aunut*lm«rTai.
5.1.5.2 Tba meaisoia in tbe bur^n* aiust cot change
by more than 0.2 cu dimun ttu3+-^jQculnierrai.
5.1.3 If the aoaJvier taJJj thrt leai«k proceilur*. aJJ
rubber ct3nu«roaf wad stopcorts sbordd b« cbecied
anUl tb« causa of tn* ieai is tdf-ntmed. L«a£iii« slopcocts
must b« dis^sa«;mbk til.
Peirrujt COi or Toluxn* (drr b«lj).
.i-Perr«al Oiftr Tolum« (drr b«ju>.
"~oC9—Pereanc CO by Tolam? id-T ouu).
^'^Vi^ Hereenc Ni br »olum« (dry b*xu).
(J.2V*— ELiUo of Oi lo Ni In (ur, v.-v.
0.2H)- Maiccu!^/ wri-rrii o( Ni or CO. Jindp<; by 100.
fl.2 P.r«nc Eicvaa ia/. CalouLaL* the p*rc*at tic^ss
(if applieaill*), t?7 •rob^tilultnt Ui<« approtmai*
luoa of cxrantO:. CO.ar.d N: (obuucfilrom ifv-uoii
1.0 or 1.2.4) uiio El4QiUon J-l.
I 100
Equation 3-1
Norr.—The *naoMou afeovt iDiiro« that «—bU-nt
air ;s HM'" cu*)i * ntii spprrci^bl*
amoonts oi N( anr present icoaJ, oil. AaJ natoral tiu
do ooc coniAia appr^ciaoU axoouatj of N it or wh^n
to JopriTal of th« Adnuoucrator, i/t r»^uire'i.
6-j Dry Mol*cuiar ^"i?ht, Cj» EquMion i-J to
CiiJculjiw ins dry 'aoJwr^Jjw w^ijnt o( tn« 3iark T^-t
NOTK.—Thf an-ivf c«l.upou ifi* nnhiJlLS
metDoJ, unlcjtt Chtt appn'timaaoa
lh« jaiijfj*'uoa of ih* .^(JjnLaiitnuor. U.i. KnviroruiiNH
tnl h*roi»*cnoa A«fn«*T. "> t* miMDl* o4 Vi-Mmj r-uiiu
v-nliin I r*n:»nt. 11 jO u( '.lif t«icn*iu:« nw-thoj,
Sort. — Th* r«f»r»t»'r ftifUiiKl fn»j" yt*W ^u«Uon*bli
mulLS whwi aoouwl ;t> ?3kiir3U'il gn jUeLca w (o
-,trcamj ihat i-oamm vati-r tiro p. ^n Thftriuf, vh-'n
tbn*ii t
mrt-bod, ai l
to «1° C '^
r^s leoiCHtr&tiirc. N»st,
ie, «itbtf by: (1)
tuuiff LUA noucur* F»rn(ii«
payctxrojnttrj: caart ud
making approonat« (xxrwruoos J lUrJc pressiui :i'
-------
Attachment E
Determination of Total Polychlorinated Biphenyl (PCS)
Emissions from Industrial, Sewage Sludge, and Municipal
Refuse Incinerators (Draft Method)
-------
PART A. INDUSTRIAL, SEWAGE SLUDGE. AND
MUNICIPAL REFUSE INCINERATORS
1. Principle and Applicability
1.1 Principle. Gaseous and particulate PCBs are withdrawn isokinet-
ically from the source using a sampling train. The PCBs are collected in
the Florisil adsorbent tube and in the impingers in front of the adsorbent.
The total PCBs in the train are determined by perchlorination to decachloro-
biphenyl (DCB) and gas chromatographic determination of the DC3.
1.2 Applicability. This method is applicable for the determination
of PCB emissions (both vaporous and particulate) from industrial, sewage
sludge, and municipal refuse incinerators.
2 . Ran%e and Sensitivity
The range of the analytical method nay be expanded considerably
through concentration and/or dilution. The total method sensitivity is also
highly dependent on the volume of gases sampled. However, the sensitivity of
the total method as described here is about 10 ng DCB for each analytical
replicate*
3. Interferences
Excessive quantities of acid-resistant organics may cause signifi-
cant interferences obscuring the analysis of DCB in the perchlorinated ex-
tracts. Biphenyl, although unlikely to be present in-samples from combus-
tion sources, can form DCB in the perchlorination processes.
Throughout all stages of sample handling and analysis, care should
be taken to avoid contact of samples and extracts with synthetic organic
materials other than TFE® (polytetrafluoroethylene). Adhesives must not be
used to hold TFE® liners on lids, and lubricating and sealing greases must
not be used on any sample exposed portions of the sampling train.
4. Precision and Accuracy
From sampling with identical and paired sampling trains, the pre-
cision of the method has been determined to be 10 to 15Z of the PCB concentra
tion measured. Recovery efficiencies on source samples spiked with PCB com-
pounds ranged from 85 to 95%.
52
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5. Apparatus
5.1 Sampling Train. See Figure A-l; a series of four impingers with a
solid adsorbent trap between the third and fourth impingers. The train may
be constructed by adaptation from a Method 5 train. Descriptions of the
train components are contained in the following subsections .
5.1.1 Probe nozzle—Stainless steel (316) with sharp, tapered
leading edge. The angle of taper shall be £ 30 degrees and the taper shall
be on the outside to preserve a constant internal diameter. The probe noz-
zle shall be of the button-hook or elbow design, unless otherwise specified
by the Administrator. The wall thickness of the nozzle shall be less than
or equal to that of 20 gauge tubing, i.e., 0.165 cm (0.065 in.) and the dis-
tance from the tip of the nozzle to the first bend or point of disturbance
shall be at least two times the outside nozzle diameter. The nozzle shall
be constructed from seamless stainless steel tubing. Other configurations
and construction material may be used with approval from the Administrator.
5.1.2 Probe liner--3orosilicate or quartz glass equipped with a
connecting fitting that is capable of forming a leak-free, vacuum tight con-
nection without sealing greases; such as Kontes Glass Company "0" ring spher-
ical ground ball joints (model K-671300) or University Research Glassware SVL
teflon screw fittings.
A stainless steel (316) or water-cooled probe nay be used for sam-
pling high temperature gases with approval from the Administrator. A probe
heating system may be used to prevent moisture condensation in the probe.
5.1.3 Pitot tube — Type S, or equivalent, attached to probe to
allow constant monitoring of the stack gas velocity. The face openings of
the pitot tube and the probe nozzle shall be adjacent and parallel to each
other but not necessarily on the same plane, during sampling. The free
space between the nozzle and pitot tube shall be at least 1.9 cm (0.75 in.).
The free space shall be set based on a 1.3 cm (0.5 in.) ID nozzle, which is
the largest size nozzle used.
The pitot tube must also meet the criteria specified in Method 2
and be calibrated according to the procedure in the calibration section of
that method.
5.1.4 Differential pressure gauge—Inclined nanometer capable of
measuring velocity head to within 10% of the minimum measured value. Below
a differential pressure of 1.3 mm (0.05 in.) water gauge, micromanoneters
with sensitivities of 0.013 mm (0.0005 in.) should be used. However,
53
-------
Stack
Wall
Thermometer"
Florisil Tube
Check
Valve
Reverse-Type
Pitot Tube
Control Box
Figure A-l._ PCB Sampling Train for Incinerators
54
-------
micromanometers are not easily adaptable to field conditions and are not
easy to use with pulsating flow. Thus, other methods or devices acceptable
to the Administrator may be used when conditions warrant.
5.1.5 Impingers—Four impingers with connecting fittings able to
form leak-free, vacuum tight seals without sealant greases when connected to-
gether as shown in Figure A-l. The first and second impingers are of the
Greenburg-Smith design. The final two impingers are of the Greenburg-Sraith
design modified by replacing the tip with a 1.3 cm (1/2 in.) ID glass tube
extending to 1.3 cm (1/2 in.) from the bottom of the flask.
5.1.6 Solid adsorbent tube—Glass with connecting fittings able to
form leak-free, vacuum tight seals without sealant greases (Figure A-2). Ex-
clusive of connectors, the tube has a 2.2 cm inner diameter, is at least 10 cm
long, and has four deep indentations on the inlet end to aid in retaining the
adsorbent. Ground glass caps (or equivalent) must be provided to seal the
adsorbent-filled tube both prior to and following sampling.
5.1.7 Metering system—Vacuum gauge, leak-free pump, thermometers
capable of measuring temperature to within 3°C (*- 5°F), dry gas meter with
27, accuracy at the required sampling rate, and related equipment, or equiv-
alent, as required to maintain an isokinetic sampling rate and to determine
sample volume. When the metering system is used in conjunction with a pitot
tube, the system shall enable checks of isokinetic rates.
5.1.8 Barometer--Mercury, aneroid, or other barometers capable
of measuring atmospheric pressure to within 2.5 cm Hg (0.1 in. Hg). In many
cases, the barometric reading may be obtained from a nearby weather bureau
station, in which case the station value shall be requested and an adjust-
ment for elevation differences shall be applied at a rate of -2.5 mm Hg
(0.1 in. Hg) per 30 m (100 ft) elevation increase.
5.2 Sample Recovery
5.2.1 Ground glass caps--To cap off adsorbent tube and the other
sample exposed portions of the train.
5.2.2 Teflon FEF® wash bottle—Two, 500 ml, Nalgene No. 0023A59
or equivalent.
5.2.3 Sample storage containers—Glass bottles, 1 liter, with
TFE®-lined screw caps.
5.2.4 Balance—Triple beam, Ohaus Model 7505 or equivalent.
5.2.5 Aluminum foil--Heavy duty.
55
-------
. j 28/12
10cm
rr \
\
\
\
\ f v
\
\ j*~*
\
\
\
\
/
\ ^~s
2.5cm O.D.
2.2cm I.D.
j 28/12
Figure A-2. Floristl Adsorbent Tube
56
-------
5.2.6 Metal can—To recover used silica gel.
5.3 Analysis
5.3.1 Glass Soxhlet extractors—40 inn ID complete with 45/50
-------
5.3.19 Porcelain casserole--Capable of withstanding temperatures
as high as 650°C.
6. Reagents
6.1 Sampling
6.1.1 Florisil--Floridin Co., 30/60 mesh, Grade A. The Florisil
is cleaned by 8 hr Soxhlet extraction with hexane and then by drying for
8 hr in an oven at 110°C and is activated by heating to 650°C for 2 hr (not
to exceed 3 hr) in a muffle furnace. After allowing to cool to near 110°C
transfer the clean, active Florisil to a clean, hexane-washed glass jar and
seal with a TFE^-lined lid. The Florisil should be stored at 110°C until
taken to the field for use. Florisil that has been stored more than 1 month
must be reactivated before use.
6.1.2 Glass wool—Cleaned by thorough rinsing with hexane, dried
in a 110° C oven, and stored in a hexane-washed glass jar with TFE®-lined
screw cap.
6.1.3 Water--Deionized, then glass-distilled, and stored in hexane-
rinsed glass containers with TFE®-lined screw caps.
6.1.4 Silica gel--Indicating type, 6-16 mesh. If previously used,
dry at 175°C for 2 hr. New silica gel may be used as received.
6.1.5 Crushed ice.
6.2 Sample Recovery
6.2.1 Acetone—Pesticide quality, Burdick and Jackson "Distilled
in Glass" or equivalent, stored in original containers and used as received.
6.2.2 Hexane—Pesticide quality, Burdick and Jackson "Distilled
in Glass" or equivalent, stored in original containers and used as received.
6.3 Analysis
6.3.1 Hexane--Pesticide quality, Burdick and Jackson "Distilled
in Glass" or equivalent, stored in original containers and used as received.
6.3.2 Acetone — Pesticide quality, Burdick and Jackson "Distilled
in Glass" or equivalent, stored in original containers and used as received.
6.3.3 Water—Deionized and then glass-distilled, stored in hexane-
rinsed glass containers with TFE@-lined screw caps.
58
-------
6.3.4 Sodium sulfate (Na2SO^)--Anhydrous, granular. Clean by
overnight Soxhlet extraction with hexane, drying in a 110°C oven, and then
heating to 650°C for 2 hr. Store in 110°C oven or in glass jar closed with
TFE®-lined screw cap.
6.3.5 Sulfuric acid (H2S04)--Concentrated, ACS reagent grade or
equivalent.
6.3.6 Antimony pentachloride (SbCl^)--Baker Analyzed Reagent or
equivalent.
6.3.7 Hydrochloric acid (HC1) solution—ACS reagent grade or
equivalent, 50% in water.
6.3.8 Glass wool—Cleaned by thorough rinsing with hexane, dried
in a 110°C oven, and stored in a hexane-rinsed glass jar with TFE®-lined cap.
6.3.9 Decachlorobiphenyl--RPP Corp., No. RPC-60, or equivalent.
6.3.10 Compressed nitrogen—Prepurified.
6.3.11 Carborundum boiling stones--Hengar Co. No. 133-B or equiv-
alent, rinsed with hexane.
7. Procedure
Caution: Section 7.1.1 should be done in the laboratory.
7.1 Sampling. The sampling shall be conducted by competent personnel
experienced with this test procedure and cognizant of the constraints of the
analytical techniques for PCBs, particularly contamination problems.
7.1.1 Pretest preparation. All train components shall be main-
tained and calibrated according to the procedure described in APTD-0576,
unless otherwise specified herein.
7.1.1.1 Cleaning glassware. All glass parts of the train
upstream of and including the adsorbent tube, should be cleaned as described
in Section 3A of the 1974 issue of "Manual of Analytical Methods for Analysis
of Pesticide Residues in Human and Environmental Samples." Special care
should be devoted to the removal of residual silicone grease sealants on
ground glass connections of used glassware. These grease residues should be
removed by soaking several hours in a chromic acid cleaning solution prior
to routine cleaning as described above.
59
-------
7.1.1.2 Solid adsorbent tube. Weigh 7.5 g of Florisil, ac-
tivated within the last 30 days and still warm from storage in a. 110°C oven,
into the adsorbent tube (pre-rinsed with hexane) with a glass wool plug in
the downstream end. Place a second glass wool plug in the tube to hold the
sorbent in the tube. Cap both ends of the tube with ground glass caps. These
caps should not be removed until the tube is fitted to the train immediately
prior to sampling.
7.1.2 Preliminary determinations. Select the sampling site and
the minimum number of sampling points according to Method 1 or as specified
by the Administrator. Determine the stack pressure, temperature, and the
range of velocity heads using Method 2 and moisture content using Approxi-
mation Method 4 or its alternatives for the purpose of making isokinetic
sampling rate calculations. Estimates may be used. However, final results
will be based on actual measurements made during the test.
Determine the molecular weight of the stack gases using Method 3.
Select a nozzle size based on the maximum velocity head so that
isokinetic sampling can be maintained at a rate less than 0.75 cfm. It is
not necessary to change the nozzle size in order to maintain isokinetic
sampling rates. During the run, do not change the nozzle size.
Select a suitable probe length such that all traverse points can
be sampled. Consider sampling from opposite sides for large stacks to re-
duce the length of probes.
Select a sampling time appropriate for total method sensitivity
and the PCB concentration anticipated. Sampling times, should generally fall
within a range of 2 to 4 hr.
It is recommended that a buzzer-timer be incorporated in the con-
trol box (see Figure 1) to alarm the operator to move the probe to the next
sampling point.
In some circumstances, e.g., short batch processes, it may be
necessary to sample through two or more batches to obtain sufficient sample
volume. In these cases, sampling should cease during loading/unloading of
the furnace.
7.1.3 Preparation of collection train. During preparation and
assembly of the sampling train, keep all train openings where contamination
can enter covered until just prior to assembly or until sampling is about to
begin. Irnr.ediateiy prior to assembly, rinse all parts of the train upstream
ot the adsorbent tube with hexane.
60
-------
Mark the probe with heat resistant tape or by some other method at points
indicating the proper distance into the stack or duct for each sampling
point.
Place 200 ml of water in each of the first two icrpingers, and
leave the third impinger empty. CAUTION: do not use sealant greases in
assembling the train. If the preliminary moisture determination shows that
the stack gases are saturated or supersaturated, one or two additional empty
impingers should be added to the train between the third inrpinger and the
Florisil tube. See Section 10.1. Place approximately 200 to 300 g or more,
if necessary, of silica gel in the last impinger. Weigh each irnnin^er (stem
included) and record the weights on the icroingers and on the data sheet.
Unless otherwise specified by the Administrator, attach a tempera-
ture probe to the metal sheath of the sampling probe so that the sensor is
at least 2.5 cm behind the nozzle and pitot tube and does not touch any
metal.
Assemble the train as shown in Figure A-l. Thrcnjgh all parts of
this method use of sealant greases such as stopcock grease to seal ground
glass joints must be avoided.
Place crushed ice around the impingers.
7.1.4 Leak check procedure--After the sampling train has been as-
sembled, turn on and set (if applicable) the probe heating system(s) to reach
a temperature sufficient to avoid condensation in the probe. Allow time for
the temperature to stabilize. Leak check the train at the sampling site by
plugging the nozzle and pulling a 380 mm Hg (15 in. Hg) vacuum. A leakage
rate in excess of 47=, of the average sampling rate of 0.0057 m-Vmin (0.02 cfm)
whichever is less, is unacceptable.
The following leak check instruction for the sampling train de-
scribed in APTD-0576 and APTD-0581 may be helpful'. Start the pump with by-
pass valve fully open and coarse adjust valve completely closed. Partially
open the coarse adjust valve and slowly close the bypass valve until 380 mm
Hg (15 in. Hg) vacuum is reached. Do not reverse direction of bypass valve.
This will cause water to back up into the probe. If 380 mm Hg (15 in. Hg)
is exceeded, either leak check at this higher vacuum or end the leak check
as described below and start over.
When the leak check is completed, first slowly remove the plug
from the inlet to the probe and immediately turn off the vacuum pump. This
prevents the water in the impingers from being forced backward into the
probe .
61
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Leak checks shall be conducted as described above prior to each
test run and at the completion of each test run. If leaks are found to be
in excess of the acceptable rate, the test will be considered invalid. To
reduce lost tine due to leakage occurrences, it is recommended that leak
checks be conducted between port changes.
7.1.5 Train operation--During the sampling run, an isokinetic
sampling rate within 107., or as specified by the Administrator, of true iso-
kinetic shall be maintained. During the run, do not change the nozzle or
any other part of the train in front of and including the Florisil tube.
For each run, record the data required on the data sheets. An
example is shown in Figure A-3. Be sure to record the initial dry gas meter
reading. Record the dry gas meter readings at the beginning and end of each
sampling time increment, when changes in flow rates are made, and when sam-
pling is halted. Take other data point readings at least once at each sam-
ple point during each time increment and additional readings when significant
changes (207, variation in velocity head readings) necessitate additional ad-
justments in flow rate. Be sure to level and zero the manometer.
Clean the portholes prior to the test run to minimize chance of
sampling deposited material. To begin sampling, remove the nozzle cap,
verify (if applicable) that the probe heater is working and up to tempera-
ture, and that the pitot tube and probe are properly positioned. Position
the nozzle, at the first traverse point with the tip pointing directly into
the gas stream. Immediately start the pump and adjust the flow to isokinetic
conditions. Nomographs are available for sampling trains using type S pitot
tubes with 0.85 + 0.02 coefficients (C ), and when sampling in air or a stack
gas with equivalent density (molecular weight, M^j, equal to 29 + 4), which
aid in the rapid adjustment of the isokinetic sampling rate without excessive
computations. APTD-0576 details the procedure for using these nomographs.
If C and M^ are outside the above stated ranges, do not use the nomograph
unless appropriate steps are taken to compensate for the deviations.
When the stack is under significant negative pressure (height of
impinger stem), take care to close the coarse adjust valve before inserting
the probe into the stack to avoid water backing into the probe. If neces-
sary, the pump may be turned on with the coarse adjust valve closed.
When the probe is in position, block off the openings around the
probe and porthole to prevent unrepresentative dilution of the gas stream.
Traverse the stack cross section, as required by Method 1 or as
specified by the Administrator. To minimize chance of extracting deposited
material, be careful not to bump the probe nozzle into the stack walls when
sampling near the walls or when removing or inserting the probe through the
portholes.
62
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FIELD DATA
PLANT,
DATE _
SAMPLING LOCATION.
SAMPLE TYPE .
RUN NUMBER
OPERATOR
AMBIENT TEMPERATURE
BAROMETRIC PRESSURE .
STATIC PRESSURE. (P,)_
FILTER NUHBER(j)
PHODE LENGTH AND TYPE .
NOZZLE 1.0 ______ .
ASSUMED MOISTURE.'. _
SAMPLE BOX NUMBER __
HCTER BOX NUMBER __
METER Al^ _
C FACTOR. _
PROBE HEATER SETTIKG
HEATER BOX SETTING
REFERENCE 4p__
SCHEMATIC OF TRAVERSE POINT LAYOUT
READ AND RECORD ALL DATA EVERY.
MINUTES
TRAVERSE
POINT
NUMBER
N, CLOCK TIME.
sSLl"c\^!c«
TIME. Kin N^
— — — ^^^
CAS METER READING
(Vml. II3
VELOCITY
HEAD
tip,), m. H20
ORIFICE PRESSURE
DIFFERENTIAL
(AH), in. II20|
DESIRED
ACTUAL
STACK
TEMPERATURE
(T,l.-F
DRYGM METER
TEMPERATURE
INLET
-------
During the test run, make periodic adjustments to keep the probe
temperature at the proper value. Add more ice and, if necessary, salt to
the ice bath, to maintain a temperature of less than 20°C (68°F) at the
impinger/silica gel outlet, to avoid excessive moisture losses. Also, peri-
odically check the level and zero of the manometer.
If the pressure drop across the train becomes high enough to make
isokinetic sampling difficult to maintain, the test run should be terminated.
Under no circumstances should the train be disassembled during a test run to
determine and correct causes of excessive pressure drops.
At the end of the sample run, turn off the punp, remove the probe
and nozzle from the stack, and record the final dry gas meter reading. Per-
form a leak check.* Calculate percent isokinetic (see calculation section)
to determine whether another test run should be made. If there is difficulty
in maintaining isokinetic rates due to source conditions, consult with the
Administrator for possible variance on the isokinetic rates.
7.1.6 Blank train--For each series of test runs, set up a blank
train in a manner identical to that described above, but with the nozzle
capped with aluminum foil and the exit end of the last impinger capped with
a ground glass cap. Allow the train to remain assembled for a period equiv-
alent to one test run. Recover the blank sample as described in Section 7.2.
7.2 Sample recovery- Proper cleanup procedure begins as soon as the
probe is removed from the stack at the end of the samp'ling period.
When the probe can be safely handled, wipe off all external par-
ticulate matter near the tip of the probe nozzle. Remove the probe from the
train and close off both ends with aluminum foil. Cap off the inlet to the
train with a ground glass cap.
Transfer the probe and impinger assembly to the cleanup area. This
area should be clean and protected from the wind so that the chances of con-
taminating or losing the sample will be minimized.
Inspect the train prior to and during disassembly and note any ab-
normal conditions. Treat the samples as follows:
7.2.1 Adsorbent tube—Remove the Florisil tube from the train and
cap it off with ground glass caps.
With acceptability of the test run to be based on the same criterion as
in 7 . 1.4.
64
-------
7.2.2 Sample container No. I — Remove the first three impingers.
Wipe off the outside of each impinger to remove excessive water and other
debris, weigh (stem included), and record the weight on data sheet. Pour
the contents directly into container No. 1 and seal.
7.2.3 Sample container No. 2--Rinse each of the first three im-
pingers sequentially first with 30 ml acetone and then with 30 ml hexane,
and put the rinses into container No. 2. Quantitatively recover material
deposited in the probe using 100 ml acetone and then 100 ml hexane and add
these rinses to container No. 2 and seal.
7.2.4 Silica gel container--Remove the last impinger, wipe the
outside to remove excessive water and other debris, weigh (stem included),
and record weight on data sheet. Transfer the contents to the used silica
gel can.
7.3 Analysis. The analysis of the PCB samples should be conducted by
chemical personnel experienced in determinations of trace organics utilizing
sophisticated, instrumental techniques. All extract transfers should be
made quantitatively by rinsing the apparatus at least three times with hex-
ane and adding the rinses to the receiving container. A boiling stona should
:>a used in all evaporative steps to control "bumping."
7.3.1 Extraction
7.3.1.1 Adsorbent tube. Expel the entire contents of the
adsorbent tube directly onto a glass wool plug in the sample holder of a
Soxhlet extractor. Although no extraction thimble is required, a glass
thinble with a coarse-fritted bottom may be used.
Rinse the tube with 5 ml acetone and then with 15 ml hexane
and put these rinses into the extractor. Assemble the extraction apparatus
and extract the adsorbent with 170 ml hexane for at least 4 hr. The ex-
tractor should cycle 10 to 14 times per hour. After allowing the extrac-
tion apparatus to cool to ambient temperature, transfer the extract into a
Kuderna-Danish evaporator.
Evaporate the extract to about 5 ml on a steam bath and
allow the evaporator to cool to ambient temperature before disassembly.
Transfer the extract to a 50-ml separatory funnel and set the funnel aside.
7.3.1.2 Sample container No. 1. Transfer the aqueous sam-
ple to a 1,000-ml separatory funnel. Rinse the container with 20 ml acetone
and then with two 20-ml portions of hexane, adding the rinses to the sep-
aratory funnel.
65
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Extract the sample with three 100 nil portions of hexane,
transferring the sequential extracts to a Kuderna-Danish evaporator.
Evaporate the extract to about 5 ml and allow the evaporator
to cool to ambient temperature before disassembly- Filter the extract through
a micro column of anhydrous sodium sulfate into the 50 ml separatory funnel
containing the corresponding Florisil extract. The micro column is prepared
by placing a small plug of glass wool in the bottom of the large portion of
a disposable pipette and then adding anhydrous sodium sulfate until the tube
is about half full.
7.3.1.3 Sample container No. 2. Transfer the organic solu-
tion into a 1,000 ml separatory funnel. Rinse the container with two 20 ml
portions of hexane and add the rinses to the separatory funnel. Wash the
sample with three 100 ml portions of water. Discard the aqueous layer and
transfer the organic layer to a Kuderna-Danish evaporator.
Evaporate the extract to about 5 ml and allow the evaporator
to cool to ambient temperature before disassembly. Filter the extract through
a micro column of anhydrous sodium sulfate into the 50 ml separatory funnel
containing the corresponding Florisil and impinger extracts.
7.3.2 Extract cleanup—Clean the combined extracts (in 50 ml
separatory funnel) by shaking with 5 ml concentrated sulfuric acid. Allow
the acid layer to separate and drain it off.
Transfer the hexane layer to a Kuderna-Danish evaporator and evap-
orate to about 5 ml. Allow the evaporator to cool to ambient temperature
before disassembly.
The extract should be essentially colorless. If it still shows
significant color, additional cleanup may be required before assaying for
PCBs. In this event, further clean the extract by liquid chromatography on
Florisil according to procedures described in Section 5A of the 1974 issue
of "Manual of Analytical Methods for Analysis of Pesticide Residues in Human
and Environmental Samples" Reduce the Florisil eluant to about 10 ml by
Kuderna-Danish evaporation techniques described above.
Transfer the cleaned extract to a 25 ml volumetric flask and di-
lute to volume with hexane. Pipette three 5.0 ml aliquots into culture
tubes for perchlorination. Retain the remaining 10 ml for later verifica-
tion, if required (see Section 10.2).
7.3.3 Extract perchlorination--Evaporate the aliquots in the cul-
ture tubes just to dryness with a gentle stream of dry nitrogen. If the ali-
quots will not evaporate to dryness, refer to Section 10.3 concerning special
cases. Add 0.2 ml antL-no-ny pentachloride with a 1 ml glass-TFE® syringe and
66
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seal the tube with a TFcf^-lined screw cap. Heat the reaction mixture to 160°C
for 2 hr by placing the tube in a hole in an aluminum block on a hot plate.
Allow the tube to cool to ambient room temperature before adding
about 2 ml of 507, HC1 in water to destroy residual antimony pentachloride.
This is a convenient "stopping point" in the perchlorination procedure.
Extract the reaction mixture by adding about 1 ml. hexane to the
tube, shake, and allow layers to separate. Remove the upper hexane layer
with a disposable pipette and filter through a micro column of anhydrous
sodium sulfate directly into a 5 ml volumetric flask. Repeat the extraction
three tines for a total of four extractions. Dilute the extract to volume
with hexane.
7.3.4 PCS determination—Assay the perchlorinated extracts for
decachlorobiphenyl (DCB) by gas chromatographic comparison with DCS stan-
dard solutions and correct this result for the DCB concentration determined
for the blank train. (Column temperature and carrier gas flow parameters
if 240°C and 30 ml/min, are typically appropriate. The concentrations of the
standard solutions should allow fairly close comparison with DCB in the sam-
ple extracts. Standards near 25 to 50 picograms/microliter may be appropriate.)
8. Calibration
Maintain a laboratory log of all calibrations.
8.1 Sampling Train
8.1.1 Probe nozzle--Using a micrometer, measure the inside dia-
nater of the nozzle to the nearest 0.025 mm (0.001 in.). Make three separate
measurements using different diameters each time and obtain the average of
the measurements. The difference between the high and low numbers shall not
exceed 0.1 mm (0.004 in.).
When nozzles become nicked, dented, or corroded, they shall be re-
shaped, sharpened, and recalibrated before use.
Each nozzle shall be permanently and uniquely identified.
8.1.2 Pitot tube—The pitot tube shall be calibrated according
to the procedure outlined in Method 2.
S.I.3 Dry gas meter and orifice meter—Both meters shall be cali-
brated according to the procedure outlined in APTD-0576. When diaphragm
67
-------
pumps with bypass valves are used, check for proper metering system design
by calibrating the dry gas meter at an additional flow rate of 0.0057 m3/min
(0.2 cfm) with the bypass valve fully opened and then with it fully closed.
If there is more than + 27, difference in flow rates when compared to the fully
closed position of the bypass valve, the system is not designed properly and
must be corrected.
8.1.4 Probe heater calibration—The probe heating system shall be
calibrated according tc the procedure contained in APTD-0576. Probes con-
structed according to APTD-0581 need not be calibrated if the calibration
curves in APTD-0576 are used.
8.1.5 Temperature gauges—Calibrate dial and liquid filled bulb
thermometers against mercury-in-glass thermometers. Thermocouples should
be calibrated in constant temperature baths.
8 .2 Analytical Apparatus
8.2.1 Gas chromatograph--Prepare a working curve from at least
five standard injections of different volumes of the DCS standard.
9. Calculations
Carry out calculations, retaining at least one extra decimal fig-
ure beyond that of the acquired data. Round off figures after final calcu-
lations .
9.1 Nomenclature
GQ = Corrected weight of DCB in nth perchlorinated aliquot (n = 1, 2, 3), pg.
G = Total weight of PCBs (as DCB) in sample, ng.
GS = Concentration of PCBs in stack gas, ug/nr', corrected to standard
conditions of 20°C, 760 mm Hg (68°F, 29.92 in. Hg) on dry basis.
AQ = Cross-sectional area of nozzle, n? (ft,2).
Bws = Water vaP°r in the gas stream, proportion by volume.
I = Percent of isokinetic sampling.
My - Molecular weight of water, 18 g/g-mole (18 Ib/lb-mole) .
Pbar = Barocnetric pressure at the sampling site, nm Hg (in. Hg) .
68
-------
PS = Absolute stack gas pressure, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 cm Hg (29.92 in Hg).
R = Ideal gas constant, 0.06236 mm Hg-ra3/0K-g-mole (21.83 in.
Hg-ft3/°R-lb-mole).
Tm = Absolute average dry gas meter temperature CK (°R) .
Ts = Absolute average stack gas temperature °K (°R).
Tstd = standard absolute temperature, 293°K (528°R).
V]_c =• Total volume of liquid collected in impingers and silica gel, ml.
volume of water collected equals the weight increase in grams
times 1 ml/gram
V = Volume of gas sample as measured by dry gas meter, dcm (dcf).
\Wstd) = Volume of gas sample measured by the dry gas meter corrected to
standard conditions, dscm (dscf).
V / C(js = Volume of water vapor in the gas sample corrected to standard
conditions, scm (scf).
Vt = Total volume of sample, ml.
V = Stack gas velocity, calculated by EPA Method' 2, n/sec (ft/sec).
s
AH = Average pressure differential across the orifice meter, mm
(in. H20).
pw = Density of water, 1 g/ml (0.00220 Ib/ml).
9 = Total Sampling time, min.
13.6 = Specific gravity of mercury.
60 *• Sec/min.
100 = Conversion to percent.
69
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9.2 Average dry gas meter temperature and average orifice pressure
drop. See data sheet (Figure A-3).
9.3 Dry gas volume. Correct the sample volume measured by the dry
gas meter to standard conditions [20°C, 760 mm Hg (68CF, 29.92 in. Hg)] by
using Equation A-l).
Vm(std)
= V
m
Lstd
Lm
AH "
Pbar 13.6
Pstd
•*• ^H
= r w bar 13.6
T
m •
Equation A-l
where K = 0.3855 °K/mm Hg for metric units
= 17.65 °R/in. Hg for English units
9.4 Volume of water vapor
Vw(std) = Vic -T
RT
std
pstd
K Vic
Equation A-2
where K = 0.00134 m /ml for metric units
= 0.0472 ft3/ml for English units
9.5 Moisture content
w(std)
m(std) + Vw(std)
Equation A-3
If the liquid droplets are present in the gas stream assume the stream
to be saturated and use a psychrometric chart to obtain an approximation
of the moisture percentage.
70
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9.6 Concentration
9.6.1 Calculate the total PCB residue (as DCS) in the sample from
the weights of DCS in the perchlorinated aliquots according to Equation A-A.
Gs = 5(G1 + G2 + G3) Equation A-A
9.6.2 Concentration of PCBs (as DCB) in stack gas. Determine the
concentration of PCBs in the stack gas according to Equation A-5.
G
Cg = K Equation A-5
Vm(std)
where K = 35.31 ft3/m3
9 .7 Isokinetic variation
9.7.1 Calculations from raw data.
100 T CK V. + (V /T ) (P. ) + AH/13. 6)]
_ s Ic in m oar
60 9 vs Ps An
Equation A- 6
where K = 0.003A6 mm Hg-m3/ml-°K for metric units
= 0.00267 in. Hg-ft3/ml-°R for English units
9.7.2 Calculations from intermediate values.
Ts Vm(std) Pstd
Tstd vs 9 An Ps 60 (1
K Ts Vm(std)
ps vs An ® (1-B^) Equation A-7
where K = A.323 for metric units
= 0.094A for English units
71
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9.8 Acceptable results. The following range sets the limit on accept-
able isokinetic sampling results:
If 907. < I < 1107., the results are acceptable. If the results, are
low in comparison to the standards and I is beyond the acceptable range, the
Administrator may option to accept the results,
10. Special Cases
10.1 Sampling moisture saturated or supersaturated stack gases. One
or two additional modified Greenburg-Smith impingers may be added to the
train between the third impinger and the Florisil tube to accommodate addi-
tional water collection when sampling high moisture gases. Throughout the
preparation, operation, and sample recovery from the train, these additional
impingers should be treated exactly like the third impinger.
10.2 PCS verification. It is recommended that an unperchlorinated
aliquot from at least one sample be subjected to GC/MS examination to verify
that PCB isomers are present.
To accomplish this, the unperchlorinated portion of each extract
is first screened by GC with the same chromatographic system used for DCB
determination except for a cooler column temperature, typically 165 to 200°C.
The elution patterns are compared with those of commercial PCB mixtures (in
hexane solution) to determine the most similar mixture.
After determining what PCB isomers are possible present, the sam-
ple is examined by GC/MS using multiple ion selection techniques for ions
characteristic of the molecular clusters of the PCBs possibly present.
10.3 Evaporation of extracts for perchlorination» For cases where the
extract will not evaporate to dryness or excessive PCB loss by volatiliza-
tion is suspected, the hexane may be removed by azeotrophic evaporation from
the hexane/chloroform mixture.
Add 3 ml of chloroform to the aliquot in the culture tube. Add
a boiling chip and concentrate by slow boiling in a water bath to 1 ml.
Repeat the chloroform addition and evaporation three times in order to remove
all residual hexane. Then further concentrate (slowly) to a volume of ap-
proximately 0.1 ml. Under no circumstances should the water bath tempera-
ture be permitted to exceed 76 C or the solvent be evaporated to dryness.
The final volume (0.1 ml) may be determined with sufficient accuracy by
comparison of solvent level with another reaction vial containing 0.1 ml
of chloroform. When a volume of 0.1 ml is achieved, cap the reaction vial
immediately and allow to cool. Proceed with the perchlorination as described
in Section 7.3.3.
72
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11. References
Martin, Robert M., "Construction Details of Isokinetic Source
Sampling Equipment," Environmental Protection Agency, Air Pollution Control
Office Publication No. APTD-0581.
1973 Annual Book of ASTM Standards, Part 23, Designation: D 1179-72,
Thompson, J. F., Ed., "Analysis of Pesticide Residues in Human and
Environmental Samples," Environmental Protection Agency, Research Triangle
Park, N.C., 1974.
73
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Attachment F
Determination of Nitrogen Oxide Emissions
from Stationary Sources
-------
11TS4
RULES AND REGULATIONS
Edteric Add Standard. 0 0100 N Prrthaie or
to -O.CDC V amrutt 0.0100 N NeOH wtjjch
1 1 .
,'l i reparation of collection train. Nfeejure 15 ml of
nrnnt ixpropanol Into U» njdiet bubbler and li
I ail errant hydrce^n peroxide into e»rh o( lie am
TO=Ji;'iUiipiEj«n. Leare the flr.il mid?«t UEpinr,er
~ jHyjable tie train u ibo-am in F!:rure f/-l- Adlujt
flb« ceaur to a tezaperanir* mfflcimt to pr*Tent «-*t*r
Pl»ce cruioed ice uid irmier around u*
igtBim.
4 1 J Uti-cberk jrccerfnre,. A le*± crwk prior to tbe
cpltot nm 14 optional; bo-w^rer. a lealc rhecr ajter the
DDLS* rm U mand*iory. The ieaJt-cceci proeedur* u
i ;ollff»i:
ffl'.o tM probe duconnecUd, piace a Tucurun (iug» at
y luiit to tbe babbler and pud * Tvruum of 230 nira
10 to.) HI; pl'-H o< nlnrh of! Ui« outlet of the flo-w aeter,
sd then. ram off *.i» pxorp. Tee Tacmim &hsil remain
uhk lor at I*ejt 30 vcondv Carefully raleue- tie
innni giun beton n'ftacx the tow nwter end to
rwut tick io» of ti' uounrrr Svud.
Otlw '••** cierk pro.Tda.-to nay be used. lubHrt 10
It iOBroTil of tie Admr Jt.-ator. U.3. EnTironinentmJ
•pcijcuon Ai»acy Tie xocedun used In Method i J
£i wiuble (or dUo»ir»rs) pucps.
6g* F) or los. At th»
condaslon of each rjn, turn off Cw porno, remoTe prnb<
(rorn th« *tact ind record tb« ftna] readlruo- Conduct &
Ink cbeci uj.n Section 4.1 J>. (Taj» l»AJt cberk b nar.i»-
urr.) Ii'i '«i^c b found. 10(4 th« u«x ran. Drain too lc«
titb. «nd fjrre tb« reicaJnint pan ol th« tnun by draw-
ijj d«an vntient nr tflrou jii tin ryitan (or 15 irlnuta
Itlhi sampUtK rau
CUan ambient ilr csn b* pnrrid*d by p&sstcz air
Uuno^b a cbarcoaJ fljtax or tKrough an e£ira midget
taplnger with 15 mJ of 3 percent HjOt. The tester OAY
cpi Ui staply ox imbltnt air, witbont punaculon.
U Simple Recorery. D'jconnect tb« LTapLacors allit
parrinji. Ducard theccntantscH tne nudget babbler. Povir
Ibi congou of tbe dW«rt Izpmxen Into s l«ai-(TM
polyfihylflneboltUfor ihjpQAnL RULM trrt thr«« mjdt«t-
Lmpiajen and tbe amn«ca3( cabea with deioruud,
d^Ill«t to tht drrin*
rao4 %cd pull a ractrora of 220 ™™ (10 UL) Be: plu< or
pineb oa Ui« outlet or UM flow rc«tcr. and tb«n Cora oil
itn ptnuQ. Tb» racoca shall nmain rabie for it i«*n
X aecoodi. Cverally r*leaae t^a Tvcnua sauxt belora
nleajuu tb< flow meter end.
Nan, callbrau LM mauttnt xyiUa (at tb« mmpoaf
floir rale nwdfitd try Lb< nutted) u follow!: crracwce
aa apprepnately o«d mt un mel«- («^.. 1 Ut« per
nrolauoa) to tb> inlet of ti» dfTtex mba. Maxa larra
lndeo*ndant e*Ubnuju rona, r**^* u '*^<* £T« rtToffi-
boiu o/ the dry ;u meur per ran. CaieaUu tn« dhora-
aoo (actor, X vwet ten mettr caiibraaoo Torooa dj-ndsd
bv Ibe dry ivi meur voiuac. bott 'olcmej adloiud to
t39 aus« reJereoc* tamperaum and cnsura). Cor oocA
ran, ind ar«rage tie resuin. U any Y TUU* deriaMi by
morv than 2 peront from tte aTerave. t^« a«unc{
57>rum u tuucnr/taal* (or UK. Ot&em». CM lie ir-r-
ace u Lb.a c&libnuon factor for snbaeqaeat UA ra&A.
i-U Past-Tun Callbrauon Cieci. Xlur acn &*Jd
tolMrle, condoeiacalibrauoncbccc u In S«e'Jon S.1.1
ilxr»«, atcept for tie foUovxnz Tur.iuoaj: (a) me leal
thtet U not us b« ooodocttd, (b) tarw. or mum reroiu-
uocu of tb« dry gu maur may be tued. ind (c) ooly tm
independent runs need b* nude. If tt* aOibraDon lartor
dou not dtriau by son Uan i pereat from Lbe Lnjiti
calibration factor (deterailntd In Seeoon 5.1.1), tbtn tie
dry I" iceur i>lam« obuued dnr^( vb« ten una
&n accepubla. If til dii tuition ficur deruia by aw*
tivn i puctnt, raakllbrmu lh« meurUK trynem u La
StcUooJ.1.1. &ad lor tb« e*Jcnlauo
glxu thenaomalarv
5.3 Kourctur. Th«ntaoieu>r c«*d not t» calibrated
bml Tolmnetnc ^*<^* and dUnta to exactly ICO ml
TlUi dekjolied. dijtllled w»Ler. Pipe tie a 2>ml allqooc of
lili Mloaon Into a li'>mJ Erlenmeyer flux, add 80 ml
or ICO percent iaopropenot and ciro to [oar drope of tbortn
bdlcaur, and titrau to a pinz andpoint ucng 0.0100 N
birtoni percotante. Repeu aad arerx* the Utratloa
tolioo. Runat'jkn^c TiLheach »nn ol samples. Repe-
al* tluuioiu nun *£TM wltain 1 percent or 0- ml.
i.
3.1 Metering Eyitan.
1.1.1 laiaal Calibration. Before !U Initial o» In tbe
Held, Urn 1-eJr chsct tie metenot ryrttem (dryic* tube,
t, pump, rtrtAzaeter, aad dry gu meter) aj
~ •Concentration TorcmM Deucnd by tbe dry (a*
meur. axncud to naadard1 conditions,
V,»-
SiC3-
Dry
djon (a.
Total yotonve of aohitlon bi wblcb Ox roKor
dlodde rvnp^ i3 contained. 100 mL
Voluma of barium percbJorau Utrant caea
for lb« sunpU, ml (a»er»<« of rtplicau
UtraUona).
Volum« o< barlom percnlorau Utraot nied
(or tb« blank, ml.
Dry cu meter-call bnibm lactor.
Eqol Talent wtl*ht of mlfw dioxide.
sampU lit tolome, ccmcted U>
wberr:
/Ci—0.3i» 'Kfasa Hg (or metric onlu.
-17.44 *R/in. Hg lor Entljah """•»
6J tHUfar dioxide cocowLrauoo. -
here:
i"»— EJ3mt/meq. lor metric nnlu.
— 7.0G1X10-* Ib/TtK). lor Entlisi nnn«-
Kqnattooe-J
7.
U Auxmbefie Enrrrinra from Snlruric Add Ujno-
t*cronr« rrmujem. L'^. DHrw. PH3. Dinaioo o< AH
Pollntion. Pnoltt Health Serrioa PnMjotlm No.
W9-AP-U. Clrmnrtail. Otuo. 196i.
2. Corbert. P. 7. The DtUrnunHion o( 8O> acd 8Oi
In F!a« Owes. JoonuJ o/ llx Lnautauoi FuaLtf 3^
5*3, 15*1.
3. Maccr. B. E. andZ. K. Dlecl.Ue«uchnx 7hie-Oa»
SOi and 3Ov rci»u. ;or: 9*-97. NoTonber 1867.
•4. Paooo. W. F. and J. A. BrinX Jr. New Equipment
and Tfduueroea for Sampling Chemical PTIXJJ« G*jea.
J. Air PoDnuoo Contre4 Ajecciajloo. ;3: 182. 1983.
S. Rom,J.J.
ErrTiioru trora 3t»iion»ry Sounzi (FaBij-Foal jir«l
8Leam Crtstra^on). EoTironmenuJ Protpcilon Ajtencrt
Research Tr_a=ti« Part. N.C. BrA-oiiOii*-,--t-024.
Doounber 1S7X
7. Anrmil Book o< ASTM St&ndarda. Pvt lU Waur.
Atmoapbenc Analyni. Amenc&n cocuty for Teadnf
and Miitrlili. P^tUdelpcoa, Fi. 197-4. pp. 40-12.
8. Knoll. J. S. and M. R. MidjeU. Tie ApoUcatioa o4
EPA Meibod 6 to Hufi SnUar Dioude Coocancrauaoa.
Enriroiucental ProcectioQ A^eocy. &ae
Park. N.C. E PA-eOOrt-7o-Ba. July 1»7J.
Mrrnoo 7— DrrriKE
-------
RULES AND REGULATIONS
417S5
SQUEEZE BULB
PROBE
FLASK VAL'
FILTER
GROUND-GLASS SOCKET.
§ NO. 12/5
5.WAT STWCCCK.'
T-60K-. 5 PT'SU
2-mrn BORE. 8-*nm OO
FLASK
FLASX SHiaO^*
THERMOMETER
GROUND-GLASS- CONE,
STANDARD TAPER.
SLEEVE NO. 24/40
210mm
GROUND-GLASS
SOCKET. § NO, 12/S
FfRBC
FOAM ENCASEMENT
BOILING FLASK •
2-LITER. ROUND-eOTTOM. SHORT NECK.
WITH J SLEEVE NO. 24/40
Figure 7-1. Sampling train, flask valve, and flask.
2.1,2 Collwtlon TSask, TwvUter bcrosttleata, round
bottom fluk, with short Deck aod 24/40 naadard Ui*r
opining, protected agaicat iaploaioo or breakage,
2.1.3 Flask Valre. T-bor» stopcock conceded to a
2V40 standard tsper Joint.
2.1.4 Temperature Gacge, Dial-type, thermometer, or
other temperature gauge, capabla of m<«5unng 1* C
(2* F) Intervals from -6 to xf C (2S to 12S* F).
2.1.S Vacnura.Line, Tubin* capable ol withstanding
avicunasol75 mm H« (3 in. Eg) absolute pressure, with
"T" connection and T-bore stoprock.
3.1.5 Vacuus Game. G-rooe manometer. 1 meter
(3ft in.), with 1-ran i.O-l-i—) divisions, or other, gsutn
^p»b'.« of measuring pi mure to wiihin -*-^-> f m Hg
(0.10 in. Hg).
2.1.7 Pump. Capabla ot evacuating the collection
flosk to a preaare equal to or less than 75 ma Hg (3 In.
Hit) absolute. • •
2.1.S Squeete 3ulb. Oae-way.
• 2.1.4 Voluoetrta Pip«tt«, 2S ml.
2.1.10 Etapi'ock and Groc&d Joint Grease, A high-
vacuum. htch-ump*racur* cbioroBuorocarbon grease la
required. Halocj.-bon 1>-S3 ha< b«en found to be eflectlve.
2.1.11 Barometer. Mercury, aneroid, or other barom-
eUr capable ot B««junag atmoaphenc pnssun u> within
2J ma Hg (0.110. Hg). la many case*, the baronucrt*
ratxliog may be obtuned from a nearby national weather
tcrvlce nation, la vMch case the nation value (which Is
tbe at*jlul« barometric prueure) shall b« requested and
an adjustment tor elevation dtBerence* between tba
wwta*/ nation lid u=pUog point shall be appUed at a
rale of miaus 2J torn Hg (0,1 In. Hg) per 30 m (100 ft)
elevaiiou increase, or vice viraa lor elevation dfrease.
2J Simple Recovery. Tbe loUowlag equipment Is
requlnd for sacpl< recovery:
2.2.1 Graduated Cylindrr. SO ml wltb 1-ml divisions.
2A2 Storage Containers. Leak-free polyethylene
2^.3 Wash Bottle. ?olyettylen« or glass. •
2-M Class Stirring Rod.
S.2JJ Ttat Paper lor Indicating pH. To cover the pH
range ot 7 to 14.
2.3_ Analysis. For the analysis, the following1 eqalp- -
2..1.1 Volumetrle Pipettes. Two 1 ml. two 2 ml, on»
3 in, «ne 4 ml, two 10 al. and one V> ml lor cub sample
acd su'i'Urd.
2JL2 PQreeUln Bnpontinii DfehM. ITS- to 2M-cU
capacity with Us (or pouring, on* lor each sample and
each nandard. The Coon No. 4500* (shaUow-lorm. l<4
ml) has b*eo found to be satisfactory, Altertuuimy,
polysethyl pentene b4aken (Na4« No. 1203. 150 ml), or
Itau beaktn (liO ml) may be used, f^Mn |\ass bmken
are used, ctchlnn o( the beakera may OUM »Ud matter
to b* pm*nt In the analytical sue. the solids should b*
removed by nitration lx» Section 4 J) .
2-1..1 Stram Bath. Low-temp*r*ton orpn^ or therrao-
tuucally controlled hot plaus kept txiiow 70* C (ISO* ? )
arc accepublo aittmatlTa.
• 2J.4 Dropping Pipette or Dropper. Thrre rKmlrrt.
1-2.5 Polytthyleo* Policcraan. Oae (or each sample
and each standard.
J.3.8 Gndoutd Cylinder. 100ml wtLhl^nldlrUonv
2.J.7 Volumetric Flasks. 60 ml (one for each satnpl*),
100 ml (one for each samnle and earh standard, and oot
tor th* working standard KNOi solution), and 10CO ml
(one).
2..1J Spectrephotometcf. To measure absorbaac* at
410 run.
2.3.8 Graduated Ptpetti. 10 ml with 0.1-nl divisions.
2.3.10 ten Paper for Indicating pH. To COTS tb»
pK note of 7 to 14.
2J.11 Analytical Balance-To measure to within 0.1
Unlro otbervls* Indlcattd. 11 Is Intended lh»i all
reagenu conlorm to the s?»-:.Bc»tlons established by the
Committee on Analytical Reagents of the American
Chemical Society, wtj'r* such spwiBcaUoos an avail-
ablevothenrise, use the best available grade.
3.1 SarapUng. To prepare the absorbing solction.
cautiously add 2.S ml concentrated HioO, to 1 Uter of
deiontied, distilled water. MlJ well and add e ml of 3
percent hydrogen peroxide, freshly prep*«d from 30
percent hydnxen peroxide solution. The absorbing
solution should be osed within 1 week of its preparation.
Do not expose to extreme htat or direct surijbt.
3^ Sample Recovery. Two reajecu «-•• required for
sample recovery'
3.2.1 Sodium Hydrotide (IN). Dissolr» 40 s NaOH
In d»ionii«d. distilled water and dilau to 1 liter.
3.2 J \Vai*r. Deiontzed. distilled to conform to ASTM
sp*c.3c»Uc3 D 1103-74, Type X At the opuoa ot ;h«
analyst, the K1CSO. test fat coidiubU orgaalg Batyc
may b* omitted when high eoooatrauoos U org-anjc
matter an not expected to Bo present.
. U Acaiysu. Vor lie aoalyiis, vtn loUawtcg rwgenU
annqtund:
3-3.1 FuminjSuUurleAeid. lStoHp«rcentbyw»i«al
tne nUur tnoilde, ULs-NOLZ WITH CAUTION.
J-3JJ r'henoL Whlta solid.
3.3.3 SuUnne Acid. Conecncrated. « pancat mini-
naunanay. HANDLE WITH CAUTION.
3J.4 Potassium Nitrate. Dried at 105 la 110* C (733
u>230°F) foramini-n«mot2boufs)UgpnotMpJip«fa-
tioa o( standard sotuuoo.
3.3^ Standard KNOi Soludoo. Dls»»T» exactly
2.1S8 g of dned potusium nitrau (K>'0t) la dtiomied,
cUnillrd water and diluu to 1 Uur with dclaniud,
distilled w&ur In a l.OCOt&l volumetric Bask.
3J.8 Working Staad&rd EMOi Soluiioo, Dilate 10
id of the standard solution to 100 ral with daiaruud
distilled water. One sililliur of th* worcuut 3uu>^ud
aolution Is equivalent to 100 u* nicroten dioude (NOi).
SJ.7 Water. Oeioniud, dlsdUed as la S«cUoa 3.2J2.
3JJ PhenoldisuUoaic Acid Solution. Dissolve 2S g
of p'ire white phenol la ISO ml coocentraud tulfuric
acid on a steam hath. Cool, add "5 cal Ivuiing tuUurle
•eld, tad heat at 100* C (212* F) foe 2 haura. Sun 13
a dirk, stoppered bocUa.
4. Procure* . '
4.1 Sampling.
4.1.1 Pipetu 25 ml ol absorbing solution lota a atmpl*
fMf, reuirdng a suAclfnt quantity for ow In prvnarvng
the calibration s'JJUiirds. lrj<>rt the f.iik T«IT« supper
Into the floii with the valve in the "sarje" position.
Aswmhie the sampling train as shown in Fiiun 7-1
ar.d place the probe at the sampling potot. Mik» svi"
that all &ttingi an tight and leak-Tree, and that all
ground ilsss Joints have b*«n properly grwjed with a
high-vacuum, higb-wcr-erature cdoronuorecarbon-
b*i«d jtopcoci: grsa*e. Turn th» Railt valve ar.d tha
PUSIB valve to tbeir "evicusta" positlora. Eracuatu
the ."ji'i to 75 nun Hg (3 in. Us) absolute pressure, or
leas. Evacuation to a pr-ssure apprachuat th» v»tf
pnsssurs of wat«r it the et^urjr t«iapena:ra vs desirsiil*.
Turn Ui« pump v»i»e to its "vent" poiir.on and turn
cfT t^.e puzp. Check for leaii?! by ot««rvins the
no=eu>r (or aoy prssurt fluitusuoo.
RDIRAL UCISTW, VOL 42, NO. 160—THURS3AT, AUGUST 13, 1977
-------
41786
RULES AND REGULATIONS
grater Una SO mm H< '0.4 la. Hr.) OT*T a period ol
1 sils'-ru is not unpubl«. and ta* fte/lc is not to b*
ur«* until UM leakage prooi*m is corrected. rrtssun
la ib* ±uk la not to ejceed 75 am H« (3 In. Bt)*b*oluu
ai tb* am* sampuax U eomm*nctd. ) Record the volum*
cj th* flj«k and raiv* (V,), to* Bask umptratun (Til,
cod the barotxuale preaun. Turn ta* OuJE v»)v*
counterctockwue to lu "purgV poaltlon tod da th*
am* with tbe pump vaiv*. Pnr?« tbe prob* and ta*
vacir.ua mo* osinf UK squao* bulb. li condensation
ocean In tb* proo* and th* iVuk »al»« ww, heat th*
Croo* utd pum until UK eonduueUoo. disappears.
Jiean. turn tb* pump valre to its "vent" paaaoa. Turn
tbe flask T»|»* cloekVa* to its "evacuate paaKion and
rtxrd the dllennoB In to* mercury l»veis >o tb* maoom-
«ur. Tb* absotau internal craaun La to* ttaik (A)
fc a)as* to tb* barometric precsar* lea taa Tnanomeur
rwding. ba-r+dtauiy turn tbe oatk. valve to th* "sam-
ple" poxttlon and permit tb* gas -jo «nt«r to* flask tindl
y«a»uiB« In tb* Bask and sampl* Un* (I.*., duct, stack)
are equal. This will usually requir* about 15 seconds:
a tanner period Indicate* a "pluif ' in tb* prob*, which-
nan a* ecmcUd b-Jcre samplui* U continued, After
eell!eU2j tie aampi*. com ta* datk v*l»« to iu "porje"
pnrtC0B u\d disconnect la* Sask from tb* sampuof
trii.n. 8na^» tb* uatk (or at least 5 minutes.
V.J2 It ta* gas beiss; aaiap'wd contains Insufficient
«r7Y«a lor the converaan of NO u> NOi («-g.. in an-
Wicabi* lubpart ai th* suadard may pxjuir* ^^"t »
nnp» o4 a calibration JM minnn o< NO Ui Ni). Ow
or7.t;ii 3o*U b< loarx^cni into U» tuJc to perajt dlj
navMsan. Oxrt«n =uy t» lutrodtmd Into u>* f"*
bT C:B o< thm neUxxlj; a) B«lon opii2j{ flMir, stub vlUi port crUndx. oirjtn. U>ea
tvacouc Ruk u> 75 «nin a? (3 in. H?) *b*otat« prosun
or ken; or C) tnj*et cxnm Into th« ftuX »Iur stapling;
Of (3) t*f%l£ft(4 BAQPUflJf Tttb. fc Tnl^);T\lTTT« ol 60 mm
Eg C In. H|) TKuum remimlM LA tb« C.uk, record
this ftaal prtoon, and tiati Tint tb« Qjuk to th« u-
cxopbcra until •-&• £a*k premn U aiaont «ou»l to
soaoopbwle prwturs.
42 Sampl* R«oTWT.!«tth«fl*ik»tiar»m!i>usuai
o( 16 boun tod tb«a ahaka tb* camnu lor t minuu*.
wawr, to tb* itopoock. Meaiur* in* voltun* ol water to
=rJO ml. Rnord tbia voltcne on Ui* ftaik.
1.J Sp«Bropbo«om«t*t CaUbratioo.
6.2J OpUmam Wartlenxin D*ierminaiian. For both
fixed and -rartabl* wartlenftn iptccropnotomeun.
calibraU acatnM uaodard oerOAvd warnenirtb o< <10
am. «»«ry ft moalha. AlttnuUlTsiy, tar nnabt* taw
loojtb 3p»eam»>ocan th* ipectnun b«rw«ea
•400 and 416 on oso* a 300 we N Oi acaodard aolaUoa (M
S»etion S.i2). II a peak do«s uot oerer, tb* speewopho
tom«ter Is probably tnaUaneUoninc. and should c* r*-
paired. Wh«n a nttk h obtained wttbin the 400 to 415 am
range, th* waTden»tn *t wnicn tbis peak occurs shall b*
the optimum wankn«tb (or the measurement ol ab-
sorbano* (or both tn* (Undardi and nmpte*.
4.2.2 Determination o( 8p»etrophoUim*ter CaJjbra.
^lon Factor E. Add 0.0. 1.0. 10. 3.0. and 4.0 mi of UM
KNd working standard solotton (1 ml -100 w NOrt to
a serial o( fir* porwlain «»«oor»Un» dlshw. To each, add
25 nU o( absorbinf notation. 10 ml deionlted. dtstUled
•nitr. and sodium hydroxide (IN), dropwise, until in*
pH il between 9 and 12 (about 2J to 3S drops each).
Bfldnmmt with tbe tTmporatlon step, follow tb* analy-
st] procedure ol SeeUoa 4.2. anUl th* solution bai be«n
avatmvt to tbe 100 ml Tatumioric flask and diraud (o
th* mark. Meamn Uw abaorbanc* o< Mch »loUon. at th*
optimom wavelength, as determined In Section &.2.I.
This ealibraUon procrdnn must be mp*ated on each day
that samples ar* aaalyied. CalcuUU the speetropboiom*
rter calibration factor M loUowa:
(.4 Sampl* concentration,' dry basis, corrected ta
standard conditions.
Open Un valve tram tl» Bask to tb* maaom*ur and
record ta* flask temperature (T/), th* b*rom*ol«
prwsure, and the diAtrmc* between tb* marrory levets
ti tt» maaam»t*». The tbaoluto inuroal prMsur* In
ts* nw'c (Pr) Is tb* barometric pretaon less ta* man-
cmewx rndiag. Traosler th* cocunu ol th* flask to a
vltri vml portions ol dtkmlud. dUUUM water and add
tb* rinse watar to th* bom*. Adjust tb* pB to between
« tad 12 by addia* socliuai byaraod* U N), drop-n**
(about 25 to U drops). Cheek th* pH or d3ppln« a
rUrriax rod into th* Mlcaon aad then touching tb* rod
to tb« pB test paper. Remove M llctl* material as possfal*
• tizg this sup. Mark ib* beupxt of tb* liquid Uv«4 »
tb* container can bo cb-jcod for Wka/te after
Label tb* ora:xnw u> claarty identity it*
and confirm wbetber «jr not aoy ample wu lost dunnt
shiptcrai; now this oo th* anatyticai data sheet. If a
aotinsble amouat of leakao bu oeeorred, either void
UM umple or us* mMbods, subject to th* approval of
tbe AdalaiscMcsr, to comet tb* naal results, Unmedi-
auiy prior to analysis, transfer the coatenu of tb*
thippiar, coatauaer to a 50*ctl volumetric &askr aad
ruvM tbe coatalaor twice with 5-ml portions of deioaiied.
' ditlll*d **Ur; Blur tb«*«
ihrM rlOM*. Wuh th* ruur with at l*art ;hr«. 15-ml
por.ions ol doonlud. dlrull*d water. Add th* filter
wejhiao tn tht onnunta of in* 'volumttno ^Mt aad
dllut* to tti* main with dtlonii*d, duuUed water. If
inllili an abxni, ib« Mlutloa can b* rrarjicrred directly
t.i tb* 100-ml volumitnc Auk and dlluUJ to th* mark
with diiooltod. dlstUM wuur. Mix th* coateau ol th*
fact t^orouitbiv, and raaasur* Ih* abserbanc* at tb*
optimum w«7tuen(th us*d lor th* nandards (S«ctioa
i J.I), uiim tb« blaiix somlion as a uro relerance. OiluU
the sunpld anil tbe blank with equal roluaas ol delOD-
tud. dlsiUrd water il tbi abaorhaac* exceeds At, tb*
ab«orbanc«olthi400w«NUisUadard (aniiKUoniJL:).
Equation 7-1
where:
.Ef.-CaUbntiea (actor
A, - Absorbent* o( th* 1(XV»« NOt standard
AI- Abeof banoe ol tb« 200^4 NOi standard
Xi-Abwrbaooe at tb* 3O>»g NOi staadam
At- Abaorbanc* o( tba 40t>w« NO> (tandard
V4 BaronuUr. Calibrau a«alnst a mercury barom-
•ter.
5.4 Temperature Oaoit*. Calibrau dial tbermonMltrs
against mercory-tn-fiajs tbermometen.
5^ Vacnom Oam*. CaUbrat* nwcbaalcal note*. U
osed, analnst a mareury maoomtter socb a» thai speci-
fied In 2.1A
5.8 Analytical Balance. Callbrau acainst standard
•weights.
Carry oat tb* ealcalaUans, retalnlnx at leait one extra
dedmaj nfor«-a*yond that ol tb* acqolred data. Round
off atmta af-er anal calculation*.
C.I Nomcnclacore.
A - Abwrbance ot am pi*.
C-CooeenmUon ol NOt aa NOi. dry basis, cor-
rwud to standard cooditlooa,
.
bctor (le,, 25/5, aiO. eU.. required
only i( sample dllntlon was aexled to redoe*
the abnrbanc* Into th* rang* o( calibration).
K t— 8p«ctrophotom«t*r catibratton lactor.
m— HassoINOtuNOiln (as sample, of.
P/- Flnaiabsohit* pressure ol (I ask, mm H( (In. Eg).
^i-lnitlal abwJut* pnason ot Oask. mm Hi UQ-
BK).
P.^- 8 tandard abaotate pressure, 7W) mm U( O.Kin.
B<).
T/-Finalab»ohjUt«np«ratnreo( flask ,'K (*R).
T/- Initial absolute temperature ol flask. *X (*R).
T«<- Standard abaalnU umprratur*. 293° K (228* R)
V.,-e*mpl* Tolnm* at tundard condiOoni (dry
basis), ml.
Vr»Volom« at flask and ralr*. ml.
V.- Volume of abwrbirjt sohillon. 25 ml.
2-MV25, tb* alinoot lactor. (K other than a IS-ml
allqoot wa* avd (or analyji*. the comapood-
ina (actor must b* sabstltut*d).
a.2 Earnplt yoreme, dry barts, correct*! ta standard
condltioni.
cher*:
Equation 7-2
°K
A',-0.3858 —^rj- for metric units
SI Vlaali Volnrct. Tbe volume ol tb* collection f.iik-
C.v.p. 7^ive combination must b* known prior tn san-
plicf. Ajwmblc Uj« r.iit and nuk valvp and till wiLti
-17.64 f-ft" for English unite
Total nt NOi p*r sampl*.
Equation 7-3
Notz.—K other than »2.Vjnl aliquot I) used for analy-
sis, tb* (actor 2 mtut be replaced by
Itf.lot.
Equation 7-4
where:
,- 10"
jig/ml
-6.243X 10-» ^^ for English unit*.
7.
\. Standard lietbods of Cbemical Analysia. «th td.
New York, D. Vaa Nonrand Co» Inc. U42. VoL U
p. 329-SO.
2. Standard Method ot Teat (ar Oxides of Nhrortn la
Oweoto Combustion Product* (PhtnotdisuUonx Add
ProredDre). In : l«iS Book o( A3TM Standards. Part 2&.
PoilaUelpoia, Pa. 1968. ASTM Dcmsnaaon, D-UOO-60,
p. 725-729.
3. Jacob. M. B. To* Cnamlcal Analysis of Air PoUnW
anta. Sow York. latencieoc* PniiliiSers, lac. I9o0.
Vol. 10. p. isi-aai.
4. B«aRy, R. I_, U B. Bcrftr, and H. H. ScisrtnlE.
Determination o< Orid« of Nttroaen by tbe PiMDOtdfeaJ-
tonic Acid M«thn«l Banaa ol iiinca, CJ. O*pt. ot
Inurtor. FL I. XS7. February 1MX.
4. Hamil. H. f. acd D. E, Camann. CoUabonttni
Study o( Metbod lor the Determination of Nltro^a
Ocd« Emissions from Stadonary Source* (FooiU Fliei-
rtrrt Steam Oecentors). Southwest Reoearei Ic5dtst»
report (or £nTiraameatal Protactloa Ajtccy. 'Himareh.
Triaosl* Park. N.C. October 5, 1773.
6. Hamil. H. f. and B. 2. Tnomas. CoDaboratiTV
Study ol Method tor th* DrtarmlnaUon of Nraroc*a
Oxide Emissions mm Stationary Source* CNide Acid
Plants). Soatirwest Baorth, lojtitvn* report (or Erv-
Tironmiotai Protection Agtncy. Pmosrrti TrUorb
Park. N.C. May 8, 1974.
MCTSOD S— DzmuczxxTtoM o» Struwc Ar™
AMD SdJTja Diozmi Eicaaio^a now
1. Proofl* and ApfUalOlH ' ' ,
1.1 Princlpl*. A ras sampte Is extracted bokii>*t!ea2y •
from th* tuck. Th* soUorie acid mist (Indndins JoiTur
trioxide) aad th* raltar dioxide an separaud. aod botti
tractions ar* measured separately by the banma-Ujona
tiaKtloo metbod.
\2 Applicability. This nutbod Is appUeabU (or tb*
determination of solraric acid mist (including soUor
trioiida, and In tbe absence of other parUcoUt* matter)
aad sultar djoiid* enusitona (rom sudoa&ry aooroaa.
CoUaboraQT* testa have shown that tb* minimr.™ •
deuetabl* ILaJo ot tha method are 0.05 milllcnu&si'cnbM
meter (O.COXICr' poubds/cublo foot) for suUnr moiid*
and 1 J m&(m> (0.74 ia-> IWltl (or raUur dioxide. No
opper limits hare been established. Based on theoretical
calculations (or 200 mlllUiien of 3 prronot hydrogen
perotlde solntioo, tb* upper concentration- limit tor
goiter dioxide in a 1.0 m> (15J It1) |u sample Is aboct
12,500 mt/m> {7.7X10-1 IbAt')- The upper Umlt can b* -4-5
extended by Increasins UM quantity o/ptraxid* soluttoa
in th* impingtn.
Possible Interferinf agents of this method an fnorideo.
tree ammonia, and dimethyl aniline. If any of tbes*
Intertving ateats an preaont (this can be deuraliwd by
knowledp ol the process), alternative methods, subject
to tb* approval o( tha Administrator, an reqniiwl
FUurable particolau matter msy b* deurtclntd alon«
wltb SOi and SOt (sab)ect to tbe approval of the Ad-
mlnistmor); how«rer, tb* proeedon Died fsr parrlcaUu
matter must b* cocsiAant with th* speclncadoo* aad
procedore jlTto in Method 5.
2.1 SampUnii. A 9cbem»tie o* th* sampUas tn
used la this method Is shown In ?l«ur* fr-k; ft is srmlUr .-::•)
to the Method 5 train except that the. alur pMldoo Is
dl(fer«nt and the Blur holder does not hav* lo M h*aud.
Commercial model* o* this train an available. Tar tboa -r
who desire to build their own, however, compete on»- •'
strucrlon details are described la APTU-0581. Chan«*s
trom th* APTDXU81 document and allowabl* mcdV
fteations to Flfure ft-1 ar* t>':
SKT. pllnj train sre described In A PT D/S74. £inc» correet
uta(« u Unponant In obtalninx vaud rnolu, aU tts«* •
should read the APTD-C676 document and adopt tb* ~
operatinf and malnunanoe procedures out!ln?«l la v,-i
unless otherwise speciAed herein. Further details and «^
iruldellnea on operation and ctaintenanee are (Sveo in •"
,M-ihc4 5 and should b* read and tollowed whenever •
they are applicable.
1U1 Ptob»Nottl*.8am«asMelhod5,9«ctJonJJJ- ^.y,.
2.1.2 Probe Uner. BoroeiUcataor quarts glfc*, «1'JLJ"?^,
beaiirt jyr.'m to prevent viable eondewatioa dune* Aff -
«a.-Bp;mj. Do not UK ra«a! probe llwrs. ~\
2JJ I'ltot Tub*, aamtss Method 5, SeeO*>oS-L3. -
MGISTSI. VO4. «S, NO. 160—THUISDAY, AUGUST U, 1977
-------
RULES AND REGULATIONS
TEMPERATURE SENSOR
417S7
PROBE
OB£
PITOTTU8E
TEMPERATURE SENSOR
THERMOMETER
FILTER HOLDER
/
.CHECK
/VALVE
EVEF5E TYPE
tITOT TXJSE
VACUUM
LINE
VACUUM
GAUGE
MAIN VALVE
DRY TEST METER
Figure 8-1: Sulfuric acid mist sampling train.
1. DtSutnlUl Titaan G»uj». Sun* ai Method i,
Ita 2.1.4.
US FQtcr Holder. BorariUe&te (!aa, with a gh»«
UUf ivippon »-d a silicon* rubber (nittt. OttMr
jlzaatenaU. e.j., T«flon or Viton, may b* oaednib-
ff tba approval ol the Administrator. Tbe holder
p'shall provide a poaiUf* MM uaiaa lr*Xa» (.-on
luidn or around lb« liter. Tb* ftltar boldtr shall
iiiod betwMo tbe ftr« ud Mcoad Implnjin. Nou:
col beat tbe filter hoidtr.
16 IsipUif!.-*— Four. aj ihown In Tlnre H. Tb«
ind thirl il^ili i* o( tb« Orenburg -Smith datra
i"rj3d*rd up*. TtK wood »nd (onrth iluil be of
Orwobun-Salth dwljc, mcdifirt by rtplaclne th«
n;»1ih »a »pproiiffi«ulT 13 icJJianut (UJ In.) ID
i lub«, tl»rlnj tn uucoastn.-uil Up lockUd 13 mm
S'.l (ram tt« bottem o( \ta lUwlf. SunUtr coU*ctloo
IBI, which &*•• tr«a ippro'td by ih« Ad=ii£u>-
or,' CUT boawd.
- M«t»n.-vj Snum. S*m« M Method 5, Section
12.4 Trlp'B&Unea. S0&frmme»p«dt7, tommranto
±OJ ( (owaurf only U i moinun content &nal• iix- 1« u*rt.)
OnUu. L»»».fr». p«i!yelhyleni hotUie,
-o»L'rtoJ
X7nleai oibendM Indicated. eJl r**«enu «J> to conform
to the spwinauon* e3l»hlish«d by the Cnamutr* on
Analytical T.t-wrntt ot tbe Amehc&n Chemical Society,
where rocfa ipctfleattoni an irailabU. OUienrtM, lu*
the b*st armllabl* (nde.
SJ BampUnf.
3.1.1 Fllun- 8am* ai Method J, Sectloo 3.1.1.
3.1 J RlUea Oel. 6»mf ai M-'.hod S. Swtloa 3.1i
3.1 J W«». Delonu»d, dw-.lied to conform to ASTM
sp«M3caUon DtlM-7«, Trpe 3 At tne or' ion o< th*
analyn. Ibn KMnOi test for ortdiiable orfitnic matter
may be omitted when hlih conanxnulonj a( orgaalc
matter are not eipccud to be preMm.
3.1. i bopropaool. 10 Ptrcrnt. Mix !00 ml of bopro-
panol witt 300 ml. of daloolxed. dljuUed waur.
NOTX.— Cxperienn hu thswn that only A.C.S. trade
lsop;oc*not 1) m:\ititelarf. TCJLS c»»« ihown taat
lioprapanol oM*m»d Ircn ccc^cxrcial gourcu occa-
caunntlly Bai ptrotide Unpunue* uat will cam* u-
roeeorair bifb raltarle add mist Beasomn«nl. TJj»
the followiag Vast for det«etlQ( p«nxide3 in each tot of
l»prapaaol: SSate 10 mi of tbe iKpropeaol witb. 10 tal
of fmaly prepared 10 permit potasiitua loviide aolatioa.
Pnp&n a blaok by lusUarly tmUnt 10 ml ol disuil«4
wtt«r. Alter 1 raiaate, read the abaor be>aee on a •pectro»
piotonettr at Ii3 oaoomeren. II tbo aSs« bane* exccecU
0.1. tbe iMpropanol gbaU not be UMd. Peroxides may bo
r&tnoted from i»prop«Aol by rcdlstUilol. or by pevna^
through a column oJ acCvKd alamioa. Hcrwrrrr. rv-
a^eav-fradelsopropanol wita sniubly low peroxide lert Is
Is readily a*«iiaol« from commercial KOTOS: therefore,
refection of contaminated lota may b« more eQciant
than following th* peroxide removal procedure-
3.1.5 Hydrotea Peroxide. 3 Permit. Dilau 100 nl
of 30 D*rm.".t bydror» n peroxide to 1 liter WIL3 deioalMd,
diftiUed vmur. Prepare (ntti daily.
3.1.8 C.-tuhrdloe.
3.3 Eaavle rucorerr.
3J.1 Wbtcr. Suoe u 3.1 J.
3.1 Anaiysix
3 3.1 W&ur. Same u J.1.3.
3.3.2 l!«propKn«l. 100 Perrtnt . . .
3.3.3 Ti-5-io lodlcator. l-(o-arsooopheoyUio)-2-ciapbr
tbnl-3 6-i;>i:Jonlc acid, diwdium so4t. or «ol»e O.M c In 100 ml ol delonlied. dlstll>d w»uir.
3.3.4 B&rlum PerchloraU (0.0100 Normal).
In "JXi tr.l deionlted, diiaUod w»nr >ind dilau to 1 liur
with lanprotMnol; 1.3 g of barium chloride dihydrst*
OaCli '-HiO) may be u»d irutewl ol tbe b«--3Jn por-
chtomte, S'.and»rciii« with jul.'ur.c acid ai in ration J.Z.
This voluuon m^r. b* proucud a«&lni\ eraporauxt at
alltimao.
FZDERAl RKSISTH, VOL 43, NO. UO—THUWOAY. AUGUST 18. 1977
-------
417S8
RULES AND REGULATIONS
SoUnm Add Starxtod (0.0100 N). Piur'iam at
=UODOJ N trtla« OOIOO N N«OH t&M
h« previously t— ^0 sttadardiud kgBlm primary
standard pouaviu&i acid prrrhtUtt
4.
: rttain » portion of each m«nt far OM u > •
bUok Mbulao. PUo* kboutaxi t o( ubc* t«l in UM CounA
. -
4.1.1 PT»I««I Preparation. FoBow th« praednn oat.
lined la Method i, Beetlan 4.1.1; filun sbould b» ia-
cctcted, but need oot b* dtaiceattd. wmdwd, or ld«na-
lied. If tbt eUa«ai iru cau b* cocaidtnd dry , L*. , mau-
lers Ine. Ul« alica g«l need oot b* w«i«b*d.
4.1.2 Preliminary Determinations. Follow tb* pro-
eKture outlined 10 Metnod i, Samoa 4.L2.
4.1.3 Prepartuio oi CoU*eeoa Train. FoUow it* p«o-
efdurs ootlinad ia Mttbod i, 6*cttoa 4.1.J- (tietpt toe
the second pamrspb tni otatr obviously luappucabU
pans) ted os»'?ljrar* 8-1 instead cJ Fljnrt b-i. R»Dlao*
tie vrond parazrapa *1Ux: Plan 100 ml at 80 penult
tsoprcpaool la tfl* ant lmpiMi.tr, 100 ml ot 3 pwetot
byilrcf *a pwoxld* ia bota tb* second aad Curd ua>
Non.— U motjmrt oootcct li to b* deUoainid Vr
liaplni«r Mulyns, wajb e*cb oX tb» first Um* Unpir-ftn
(pliMfctnorOUK aolddoa) to U>« M*raa 0-b t *od nraxd
tarn wii«liu. Tt» i»«iKbt of to* «iUo nd (or siUc» ttl
ploj ooouin«r) mod »l» bo dMamuua to Ui» HMnat
0-4 » mod recorded.
4.M Fntcst L««k-Ctn)dt Praosdar*. ToUo* tb«
bane pnndun ouUiowt la Hetbod 5, SKOOD 4.1. ti,
Doting tax tit prate bwxr io«U b* «d]usud to Uw
T^ntt^mi} td&ponton n^olnd to pnTWt ooade&a**
ttoa. tad tin tbM Yecbtz* 9uct> «.*•••• plwgiog UM
Inirt to Ui« Uier bolder • • V" so*U b< noticed br.
..... plcniix U» iaM to to. But lapui«ir • • '."
Tb* pnucTUu-cntek 1> optloo»L
4JL5 Tnln Opentloo. Follow th« bade pnecdom
omllo«d la Melbod 5, Section «.U. In coaloaeooo -vita
on tibMtamOtf toth«on« la Tijrart ft-2. Tb4 nmptint
nu 3^*11 not «c«nl 0.030 JB*/OUI (1.0 ctn) danac UM
ran. PenodiokQr du-it>t in* i*n, obw-ri to* ooaixctUMi
Uir prab« tad Ant Impinjcer (or ncxui o(
U It dog* orror. *4]us Ui» prab* bamur
d to to* Tr>tr.>fWMt« tAmp4ra£Qz% nqatxwi
to pnTvnl coodwuttioo. II aa)
tooted tb* xpKliad nU, UM U*t*T >b*U clUMT roid til*
ran or 30*11 pUa to *orract to* «apl* Tolaia* *• oat-
Ua*d la 0*eflott4-3ot Mctbod &. Tmrn-Hii'tiT ttttf oonw
pootot chaotu, w«t&iid»tory) leak-
ehwJc M la S«:uun 4. 1.4.3 or Metaod 5 (wilti tpprophau
moc2>1, vitb tbt prabidiMonaiYbM),
po—t tte rrt of tbt train, by drm»Tax clr*a
« .'M.-j-.t ill -.hrai;;.', th* «m«a lor 15 ciinuus *t tS«
a • •:.-%* flT» rut Ox-d lor «uapUs(.
Nqn.— C'la«n tir.tl-nt all coa bi prorldtd by p«ula(
all ti;ou7h & ch.vcukl iUur. A*, thr option ol tit tnUr,
c.Tihi«at &;r \wi Jiouc d^*i"JnK) ^^7 t*« U3*d.
4.1.4 CtkttUtioa ol Purnnt L«akinctie. Fallow tbt
'
•i.li Coaulnv No. i. u t nol^an ceouat uuiru*
Flgur*<-2. Field dau.
li to be doo*. w«i|b th* tint Impinfv pln«ue5tOJ|Uidrecord tbi» wjjght.
tn« contents o( tht firs lapin«r to t JA>cJ
cylinder. Rirvs« the probe, ttrrr impingi-, ill
! iltssw»r« brfore tbt filter, tod tb« Innt Sai.'
of tbt ftlUr bolder u-tth SO p«rce=t t3opror>tr."(. Add tb*
rtoM tolutlon to tbt cylioder. D'.luw to liO nil with 80
percent isuproptaol. Add tb« filter to tht Klutton. =ux,
tnd Uvultr to tbt jtorut eoauiaer. Protect th* wluzor.
t(«lr.n tTaporaticn. .v*vk tbt level ol liquid oa btt
conulntr an-', identify th: »mpl»coat*aner.
4 J-3 Cont«lc;r No. 2. If a rcsuture conten; iriimi
Is to be don*. w«uh tbt second ind t^iid ins'j-.j-rj
(plui conunu) to thu o»--est OJ> | ted record [hn«
•vrti^au. Also, wtivh. tht sp«nt silica (el (ot aiTca ;•!
plus tmpi.-.:r-r) to the a««nst 0 J j.
Tniuler the solutions trora tht ncond tnd tbird
taplfueu to t lOOCvinl undiuud cylinder. Rics* til
cotmectlnx tltsr^an ita^ludintbtckbtlt ol (Uitr holder)
b«tw«*a Uie tlur uxl Uiic* etl Us plater wkUi -Wnr,.;i«<1,
dlstiu*d wtur, sad edd this rins* inror to tb*
Dilate to t volume of 1000 rrj vrttb dtioau«d.
wst<7. Transfer t^e sotouoa to t stor&se coQt*latr. Mark
tb* lerel of liquid on tb« coauioc. S<&1 tiid ideatirjr U*
umpl* coattiner.
4J Analysis.
Sou tac icvel ot liquid ia cont*ia«mtad2. tad no-
tea winter or not my sample vu lost durvcg ihlp-
— er.t; nou this oa tht aaaiytical dtu sh«i. II t aottc*-
tole &ziou=t of Ib&^u^t bu occurred, either void dt
SB.— p> or UM rjettjdj. sublet u th« tpproTtl of tie
ii-.c'-ei.
4J.1 CoQtiiatr No. 1. itatt tti container boldly
teoprop&nol solatioo and tb« filter. If tb*
-
drops of thorin Indicator, and ::fM ta* tttruiou
Tim t Mcocd tUquat of nunpl* ted iT«r»i« th* UtriUoo
FEOIZAi REO1STU, VOL
-------
RULES AND REGULATIONS
41789
T*!DM. lUpUcaU y trailon* meat tpw wtthin 1 peraoi
or 0.: ml winch* w LJ greater.
4JL2 Coauuwr No. 2. Tbcrtwjiily *"'« tb« «"i"*""
In th« container balding tbe content) of UM wcooxl and
tuird Lsslnicen. P1p»tte * lo-ml iliqaot of jampi* Into •
230-ml ErUameye/ (Luk. Add ml o< bopropanol. 2 to
4 drops of taonn IniUcttor. and tltnU to a pink end point
nolnc 0.0100 N b«rlQm p*cr^Lbv«£«. Bepeat th« tftratiAa
wttb. a oeooad aliquot o«jampU aad armr* tn« tt&atida
rainae. Replicate dttatlooj man agrv wimia, 1 p*rmt
or 0-3 mi. wblefMnr li cnacer.
4.3J Blanka. Prepew» blanks try adding 2to4drep«
o( tnorln Indicator to 100 ml at 80 percent bopnpual.
h. hl«Jlk7l In th« ..TTI. nr .nr...
M Gallant* etroipmaiit tains t&4 pnradnm imei.
fled In Uu foUowtn* section* o( JUtnod 5: B— -H™ JJ
(suuilaf lyjum); Section i-S (umpcratzm gaogM);
Section S.7 rbaromeur). Nou toat tb« recommended
lau-choci: of tb« mturiox rjTWm. d«cr.bed la S«cOea
&4 of Mjtbod 5, aljo appUM u tHi_< miUxod.
U BUadjkrdlM the Danraa pcrchknu nlotlao vith
23 ml of n«ndant saUurld acid, to wtUcn 100 ml ol 100
ptrant ijopropaaol bu brna »dd*d.
8. CslnlaOau
Note.— Carry cnt csicnlAUotu nUlnlct at U>ut oo«
ertra decimal imr» txytiad tbat of UM acquind ti'*
Hoond off Oinrr« att«r n^mj <»*i/-nUttOT^
(a Nnm«ncl»tcj».
/4.-Cro«»-v«nloD»l ana of ooiila, EI> (ft1).
vapor In tS« zu ICMHI, proportioa
flncladlnt SOi) cooowtntioa.
t/dvm Ob/dacT).
CBOi-SaJm- dJonde coacanlndoti, i/dxm Ob/
cbc/).
7—Perwnt o(l»lcin pnaan, mm Hf (In.
TOO
Hi
.
?"l*d-8Undird
03.92 In. Eg).
I". - ATertio ibaolnui dry ru
(>M Flra» S-2), • K r B).
T.— AV«JTUJ» abwluU jtack jilUmpaniom (M*
Fl)itir»S-2).' EC H).
Tttd-SUndxrt abwlut* Umpcraton, 293* Z
(53« B).
V.-Volun« of sampU lUqoot UtraUd. ICO ml
for H>SO« and 10 ml lor SO >.
Vj.-Total Tolomiof liquid oo CUcUd In l2pln««n
and tlk» tti, oL
V.-Voltcnu o< rai mmpl« u mc*Jond by dry
ru = m«t«r camaM to ninrtird coadiUaai,
».— ATETSO T*at> ?*» nlodtr, calcalat«d by
Mnbodi. Eqoanon2-«. crcji* data obUincd
from Metiod 8, m/Tne Itttxx).
V»ln- Total Tonxc* of wltruoo In wblch the
mitortc ixld or lallnr dloilde sunpl* Lj
contaiaod, 2.V ml or 1,000 ml. rnpKUTtly.
Vi-Volcan* of bariara porcnlonu tiuut tuvd
for tb* saxnpiA. ™*- .
Vit»Volam« of b&daa perchJonU tltrmnt tatd
for tb« blank, ml
y- Dry s«J met« odibrttion factor.
^W— ATSITU» pressure d--T>p tcroa orLOc* met«r,
mm (In.) HpO.
9 — Toul sampUnf ttm«, min.
13.8-8 p«clJlls trSTlty of UMreury.
» Cooraniorj to p«mnt.
no dry »« m«*r t«mp«r»tur» and
prunin drop. €•• data 3be«t (Tlf ur* ft- 2).
8-3 Dry GUJ Volume. Comet tb> lamplt Tolcun*
mtasurvd bf tbt dry xaJ mrl«r to standard conditionj
Car C and 780 mm Hj orM* f and 29.32 tn. Hj) by nsifl|
Equtloo i-1.
13.6/
. P^-KAtf/13.6)
Equation 8-1
, Hj for mitrlcanJU.
-17.44 'R/ln. HI lur EajlUJi unite.
NOT!.—If the Ua* rmte c^^er^f dncrlt-d la P«ction eJ of Metbod i), or ihall
at* tte u»nip»F
1. Atmo3t&Gri£ ^misilooa CTOTH Solfnric Add MACD»
Jactnriiii ProcsOM. OJ. DHEW. PH3, Dirlilan of
Air PolTotioo- Public Healtb Serrice Pnbliollnn No.
9W-AP-13- CLnclncsti, Ohio, 196J.
2. Corbttt. P. F. Tbe D-temunilkiQ of SOi and SOi
In Floe Q&M- Joom&l of tbe Iiun raw of Fuel.
1901.
X Martin. Robert M.Constrocttoo Deta3a of
Soorca Samp ling Equipment. ED TITO am en Lai Protection
Agency. Researcb TnanjU Pali:. N.C. Air PoUntion
ConDTil OCcs Pablteslion No. AJTD-OM1. April, 1971.
4. Pirtoa, w. F.and J. A. Brtai. Jr. Ne» Eqolptnaot
and TecboiqaM for SitEplinjs Chemical Pmcxa Gasea,
Journal of Air Pollution Control AJaocUtLon. /3.-183. 1»«3.
S. Bom, J. J. Maintenance, Calibntloo. and O wralaoa
of Ijotuetio Source-SaapUn« Equipment. OQc* of
All Protrami, Earlronmental Pro^ction A««ney.
rUatarcb. Triaafle Part. N.C. APTD-Ci7S- March. 1972.
j. H.mii £L y. »ad D. E. CamAnn. Collabontir»
Stadr of Metbod for Deteraiinadon of Bolfar Dioiid*
Emlislonj from Stationary Sourow (Tond Faal-Flred
Btecm Generator)). Enrtroam»cuJ Prot«ilOQ AisncT.
R«»arcli TrLinjl* Park, N.C. EPA '140/4-74-001.
D«««mb«r, 19T3.
7. >nnn»l Book of A9TM SUndarda. Part 31; Water,
Atmoapherlc Analrilj. pp. *0-(2. Amfrlcan eoci*tr
for Tanln< aad lUurlalx Pbiladalpbia, Pa. 1»74.
• • • • •
<~ra. Ill, 114. 301 (a). Clean Air Act. »c. 4(a) of Pub. L.
Sl-604, >4 But. 16&3; »c- 4'a) of Pnb. L. 91-604. W Stat.
1SS7; MC. 1 Of Pub. L. 90-144, 81 Stat. 504 [42 OJ.C.
Ui7c-«, l§STc-», l*S7g(»)).)
(rBDoc.T7-13S08 Piled 3-17-77; 8: 43 am]
FJD£«AL RECISTf*, VOL. 42, NO. 160—THUXSOAY, AUGUST 18, 1977
-------
Attachment G
Determination of Particulate Emissions
from Stationary Sources
-------
RULES AND REGULATIONS
M, wrt It lnu> '.b«iuck, ud
lample at a camum rue ine
ourut OJ ml
3.3 ral(mi*fum« TK^a^l—rcfrtJ^ nfrtth'HI p***^"t.»c-
carau mautur* dxUEmtaadm. arr rvM coll«cud. Tti«
lollowtnf oqtmiiam xUqtcu«i7 •«jnui> tn* moutar*
amtcnt. for tb« porpaM a( d«^iiunic« Ivluneuc sam-
pling r»ia saciinct ^ .--" •-t»I— \i«
SJ.l Noromci«Ou»-r- --
>; profnnleo. br ^oliimr. ot
tn li»-CM tuxam IOTUI; th«
. """»
ion by
3 J.4 AppraiiauU
.
P.- Abootote
barametrio.
Ow> dry K" oner.
T60 mm H{
l in. Ht)
. i—
ru anbun, aoern (mm HE)
(or Tn«ir*e omu wid 21.45
Til) lor
»t mciT. "K (*R)
- tunprraran, iO* E
(528" B)
r eontmu, mi,
n(»nu, ml.
br drr r" ffimr,
dem (dd)
V.l.m-Drr ru-nteo* mM«iml b? dry m tn»t«r.
comcud t»- ntadard ooodluou, dxm
(djcfl.
Vr.<(ur>m«ur). Tb« rtcommecdeJ leak
check o< th« mntanm Jysu™ ( Section i.8 o< Meuvxl i)
&ljo ftppi]«a u> tb« re/er»fKv ^ipLDod. For tbe apprann»
tlon method. UM tbo procedurw onillned in Secdon 5.1 J
o/ Metbod fl ui caliDrau Ui« metering 5T5teiru and- Ui«
prondon ci Metood i, Sectxm i-7 u calibnu ti«
baj omet«r. ' ^
1. Air Pollution Engineering MAUO»I (Second Edition).
Danlelacn, I. A. (ed.). U.S. Znvirarunenm Prot«3on
Ag§n ayallible. For chaMes from APTD-06S1
and for aliomble modiAcaLlona oif the train ohovn tn
Figun £-1, M< tbe following sabwcnoro.
Tne operutlnc and maintenance pr«r*dur»3 for the
sampling train are described In APTD-0578 (Cltacion 3
In Section 7). Slnee correct uaaje ia Important in obtain-
In It ralid rwalo, all users sbodld read APTD-iSTJ and
adopt tbe operating and rnaintenanc* procedures oat-
lined tn it, nnJesi othenrlse specified herein. The tan>
train consists of the following components:
FIOIRAL IECISTH, VOC 41. N
-------
RULES ANO REGULATIONS
4177;
TEMPERATURE SENSOR
REVERSE-TYPE
P1TOTTUBE
IMP1NGER TRAIN OPTIONAL, MAY BE REPLACED
BY AN EQUIVALENT CONDENSER
CHECK
VALVE
VACUUM
LINE
THERMOMETER
FILTER HOLDER
HEATED AREA
TEMPERATURE
THERMOMETER
/
PtTOTTUBE
PROBE
STACK
—•WALL
IMPINGERS ICE BATH
BY-PASS VALVE
PITOT MANOMETER
ORIFICE
VACUUM
GAUGE
MAIN VALVE
THERMOMETERS a
DRY GAS METER
AIR-TIGHT
PUMP
Fjgure 5 1. Particulate-sampling train.
2.1.1 Probi XOCL.
ea si**l CIA or fl*m with
limrp. tapered Waging *dg*. Tb> acgl* o( tapur
bo <3P and Lb« txxr laall b*oa t&toutaide to preserve
a constant Uiiora»J *;.—.-.. Tb« probl* anal* s&all b»
ol lh« buttoa-noak or elb»w dMitn. ucLaa oUxnriM
ipeelned by UM Adnuumur. U ""^* ai sainiea
ttteel, Ib-e ooule. thall !M coaxCTJctad from •*«™i-tt cufc-
let: OUuraauruui «' coartrucdoo m»y b* used, subject
Co the apprwnl ol tbe. Artminrtinmir.
A ra&ge o< aoul* ute* suitable lor i»lda«as ««"'t'""t
Ihould b» avallAbl*, » t.i B-32 to L27 era (H to }4 la.)—
or larger U higher volume. sampling vaiai an r«d during
nmpUm. prob«5 coiuu-Jcl*d oceordic* to A.PTD-OSM
tnd uuiiztot it>e calibreuoo CU.-TM o( APTD-G57B (or
C*iibr3le>l nxcrd-nt to Cie practdurt outlined In
) »TU &• eoruidtrid «ff piablt.
j aboui 4SO* C .900* ?)•
quaru liiun sluOi M im. Imoloy *:.\." or oilier
rurroilon rMisiucu m«uuit madt ol»«aojleu uibmK may
b« iu* Admlniaintor.
•.' l.J r'ltol Tub*. Typ« a. 1U ^Mcrb»d in 6liall W auu'n«d to th« prcU tu
orutant monitunnr of th»
plao> ol (tit pltot tube siiaU b« «im Ttth or abtm tb«
cu* ouurn«d in S«cooa 4 at
U*tbod 2.
2-1.4 DUIaranUa. Prusur* Gtuga. IncJlatd E3*nnn-
•ur or equinum den- 1 krvo), u sacribwl is Section
2Jof Mttflod2. Oo*manam*ur stall b« iu«4.arT«k>city.
Mtniloo o lrad« ni3«i or irwrlP/.- product do*« ooi"
r Mtiuiitt tndorMmtni by Ibe Enriroaaitiilal 1'ruioc-
:.ia A^eocy.
pzanux
2.1J FUter Hoider. BorofiUau (lao, with s rtaas
bit flltw soppon and a sliraoc rubber fuktt. Otbcr
matnialj of construction* (ex., nles> Rm, Teflon.
Viton) may be used, subject ui ippnnl oi ibt Ad-
mloiaruor. Tbc bolder das en stall pnride a pcoiUTi
Mai agsinst lnkM» L.-OOT tb<- oot*ide or aroond '-ir (Uurr.
Tbe bolder, «h*U b< atucbed immediately u UM outlet
ol tb« probe (or cyclone, U used).
2.1.9 Filter n»dn« Synem. Any beulng 975t«9a
espabl« ol maintaining a letnperamrr arouod tb« filter
hoMer durinf sampung o. 13>±14* C (l&±y.' F), or
sucb otber tcapi-rature as specified by an applicable
sobpart ot tb« staadards or approred by tbe Adminis-
trator for a particular application. Alternatively. l£e
UBtfr ciiy opt to operate tbe equipment at a temperature
lover than thai specified. A temperature gauie npabte
ol measuring tftnpmiure to wiitiin rr* C (.V** F) shall
be lonalled so thai tbe lemprrauire around tbe filter
bolder con be regulated and tnooilo.-ed dunng sooiplin;.
He»ung 'njer) may b<- usr>l. j'-'.':«t
to tb.' i-iprovil o: the AJniuiUirator. Thr rtrsi »n 1
jcconj liupincrrs shill conuun Vaoim (iui:iti'.iff o;
w^tir (Six'ilon «.1.3). tV ihint ?hali ty emi>:v an-J the
fourth :;-ht o( siUt-a M. or
•qulralcat d««iccanL A thrniioroLtcr, capable o<' ir.rH^ur-
tng temperature to irithln 1* C (2* H itaO. b« placed
at tbt outlet of iba fourth Implnger for mauumog
purvonea.
AltenxadTely, ao7 VT^tera that cools the saMnpi« g»a
stream aod a&rvi mematmoavnt o^ tbe war oo«den5ed
and molAurt leanng tat condenser, a*ca to vtthia
1 ml or I g may b» used, subject u ib* spproral ol tbe
Admlolstrauir. Acceptable mewia are to mauure ino
coadenMd »»i«- e:tb* F) ao4 determining
the vdghi gain. •
U aeana other than silica gel an used to determine
the amount of aoUtore leannj Ittf coadeasrr. ii J
recommended IhAt siUca scj (or equivalent) sxill b«
used between tbecondeaser srsuc aad pump to pre-rmt
moisture condensation In the puropoad mtenrnc derice9
and to avoid tbe nerd to mafrf correctior.a for mocsuxre la
the aetercd voiujae.
NotJt.—If a detemlaatlon of the portfculate csaner
collected In the impingm is drsiml in additloo to mois-
ture content, the impinger l\-utm described at-ove shall
be usod. without modification. Indirlctua. iuia or
. control agencies ren/Jtnn* thii mformMion thill b«
cont^cxed as 10 the saaple iixutery and aaairsis of the
lopnissr contents.
ilJ Metrnnf System. Vacuum Baojr. \rak-'r»
pujnp. thermoccters capablr oi measunn? tempi-return
to»ituin T*C (5.4* F).dry gas metercapable of mewunaj
volume to within '- p*rcvnt. and rv-laitrd ^luiprnejtt. as
•bo'jrn in Fijur? i-l. Otber meteriag syslcros rapaWe of
maintaining sampling rates wiibin 10 IHTCTOI ol ao-
tiiietic and 01 determinin*, sample votiunr> to within i
perwni aay \>» used, subjrct to the apprpv*! o the
Ail:: .^s-.rator. \Vhrn tbr meienni: smcro is u»rd :n
cnn;jnctioii ^ii!i a pilot lube, ihe system staii eaabl*
cbrt:'i' oi iMSii—tic rain.
#.:i-!>l;i'Str^u;ii'.ilizinjmrtrrtnjsystenisdwirntrt for
h.--^ T flow nt-3 troji thai dt- met.
•J.:.'.» B^rom-'t-r. .Merrury. aneroid, or nther Ijaromeier
eiir^iU- o' rv.eosurini atmosphcnc prw^ure Lo with.n
1;.^ :nm Us (C.I in. He). In many ca>?!>. Ihe barometric
f.i-i:!i; may b» 9fx.oir.rt from n owirby natior.ul «-miuer
s-.-rr.cf siution, in v,h-ch cu» Hie suuoo v^lue (wtiicli U
FeOiRAl RECISTSU, VOL 42, NO. 160—THURSDAY, AUGUST 13, J977
-------
4*773
RULES AND REGULATIONS
th« absolute benraieCrte prmsun) shall b* miuaited tad
an xliustment. tot el^vadoo ditferencea tMiwem U>«
wnuner station and sampUa point saatl b« applied at *
nie of minus ii mm Hj iO_l In. Hg) per 30 m (100 ry
i'l»vaaoo Intireaw or vio* versa lor elevation deensa*.
•2.1.10 Q«J DOUICT Determination Equipment.
Temperature s*aaor and preasun ffftuf*, as described
in Sections 2.3 and 2.4 of Method 2, and gas analyur,
I (necessary. as described in Method 3. Tha tempvratun
*»nsor shall, preferably. b« permanently attached to
» n* pitot tub* or samptine orub« in a rtced configuration.
such that th* tipof thes*Mi3or?rt*nd3 beyond the leading
edze ol tb* prob* sheath sad dan not touch in 7 metai.
Alternatively. th* senior ir.»T t>« attached lost prior
to us* in th* n-id. Note. however, chat if ta* temperature
wasor i] auarlied In the fluid, tb* sensor must b* placed
in an imfrfensiiro.fr** arrangement with respect to th*
T?r*» 5 pitnt t'ibf openings lire Method 2. i'irur* 2-T).
Ai & second aiierttaave. if a difference of not more than
1 percent ui tbe average velocity measurement is to b*
Introduced. the tamperature ;rauiie need not be attached
to tna probe or pilot cub*. (This alurnatiT* b subject -
to too approval of tn« Administrator.)
2,2 Saispl* Recovery. Tb* loUowinij lUms- ar»
needed.
2.2.1 Probe-Liner and Probe-N'otil* Brasbei. Xylon
crutl* hnisbe* with stainless 5tml wira handles. Tb*
prohe V>r.^b shall have extensions lat least as long as
the probet of stainless si*rl. Nylon, Teflon, Of slmilirly
Inert maunal. The crushes shall b* properly sued and •
sbioml to brush out the probe liner and nouJe.
2-2.2 Wash Bottles— Two. Glaa waah bonlea are
re*ommended. p»ly«thyl»na wash bottles may be used
at the option of the tester. It 12 recommended that acetone
net b« stored In pcly«tl:yi«n« bottles tat lonccr than a
month.
2 .2.3 Glass Simple Storage, Containers. Chemically
resistant, borotiiicaia giau bocti*s. lor acetona wasbea.
£00 ml or 1000 ml. Screw cap Imen shall either be robber*
barked Ttaon or shall b* coruLnu.-t#d so as to b* ieak-(re*
and resistant to chemical aft art1 hy acetone. (S'amrw
mouth glass bottles baT« b~n found to. be lea proa* to
AlUmaUTcJy, poiyethylnM boctlea may b*
.
2.2.4 Petri Dtsha. For alter samples, fjan or poU-
etbyiece, uixleas otbenru* speei^ad by . the j^doun-
Isuator.
2J2.i Graduated Cylinder and/or Balance. To meas-
ure condensed crater to within 1 mJ or 1 g. Cradnated .
ryunden ihail baire lubdlTisions no crrater than 2 ml.
Moat Ubomtory balancu are capable ol weighine. to the
nearest O.o t or-lm. JS-ny ol theM balsncea is suitabl* (or
cs* acre u>d in Section 2.3.4.
2.2.6 Flanic Storaf o ConUista. Air-Uiht tOBtainerj
to store silica gel. ,
22.7 Funnel and Bubber PoUmnan. To aid In
transfer of silica |el to container: not neeeEary U liUea
{el Is veiihed in the field.
2.2.S ? utmel. Clast or polyvthleea. to aid in iampV*
recovery.
2.3 AnViyils..?or analysis. tb*!ol2owiaf equipmentls
needed.
2.3.1 Glass WeigblnK DWwt
2.3J2 Deaiccator.
2.3.3 Analytical Balance. To nwawr* to within 0.1
rrj.-
2.3.4 Balaoca. To mmiore to wltUn OJ f.
2.3.3 D«Jctrj. 2jO =1.
S. 3.S Hydrometer. To m**oura the reUtlrt humidity
of the laboratory earlromneoc.
2.3.7 Tcmp«rinir» Cauice. To measure the tem
tnro of the laboratory env;rootneai.
3.1 SaaplSnt. The rc&;;nts used iu sampUuf ore *s
(nllowi:
3.1.1 niters. OUra Cb-r flltwj, without onraala
binder, exnibltiax at luut 9u.9i percent ejtciency ( <0.0i
percent p'ne'.rMmn) on OJ-nucxon dioctyl phthalate
snjot* partldM. Tbt Uter «fl\civncy tnt shall be con-
tfuct"! in &c-71. Tcit dMa from the sappU«r'i nullity control
prosrusi are fulncieat for this purpose.
3.1.2. Silk* Oel. Indicattnc 'vpe, 8 to 16 mnh, I/
pmvitiusly uvd. fry at 17S* C (IXr1 F) for 2 boars. New
silica Rel m&y be used at receired. Alternatirply, othrr
tyix4 uf ds '.e^uiraltot or b«itfr^ may be oded.
5UO]*1**: to thr ^ppruT^J of the Admtnisxrator.
3.1.3 Waur. Vt'hen analysts o( the. material cuojht In
thr Lmpmufr* ii rmuir-d. daulled wil»r shall be used.
Ryu blanks pnor to luM ua« to «iiminan a high blank
on t<\>i '* ot nopcock eruie oar be uied, tub-
Jtct :o f.* spprorrvl o( thr \djniiuttraior.
.1.2 rj:!inl«.K«corer>-. \ceton«— roionnl gnje. 4 b<>ttlfs from meial contiiincrs; thus.
.-\cewre r-!"\n.'.s slia.'. h« run prior to field us* and only
ucetone w;v,i low blank vr.iuas (<0.001 percentl .ihAll be
ui'-'l. In tio C4*< shall a blrvuk value of creator than ij.OOl
> :-"*nt of the »eii;iit rl fr>'loni! UifJ he subinuttd from
i. .••««..;.. * filtcn ta thes*
eoatainen at all times ewepi donog sampling and
weighiot.
Desiccau tht alters it M±5.r C (M±IO* F) and
ambient pmsnr* for at least 2t hours and weigh at in-
tervals of at ieut 6 hours to a constant weight. I.e.,
th« length of probes.
Select a total sampling time greater than or equal to
the. miniaium total sampling time specified in the ten
procedures for the rpociiitc industry such that (1) th*
aiunpuag time per point is not less than 2 min (or some
greater lima interval as spudded by tha Administrator I.
and (2) th* sample volume taken (corrected to standard
conditional will'iicnd th* required minimum total gas
aaapl' volume. The latter is based oa aa approximate
average sampling rate.
It is recommended that the number of minutes sam-
pled at each point be aa integer or aa integer plus one
h»ll minute, in order to avoid timekeeping errors.
In torn* circumstances, e.r., batch cycles. It may b<
n<*«asary to sample for shorter times at the traverse
points and to obtain smaller ;as sample volumes. In
these cases, the Administrator' i approval must first
tx obtained.
4 1.3 Preparation of Collection Train. During pnp-
aration and assembly of the sampling train, keep till
opvoings where contamination can occur covered until
Just prior to assembly or until sampling Is about to bofin.
Place 100 ml of water In each o! ihe rest two uupinjen.
leave the third Unplnger eznpty, and transfer approii-
ciateiy C'JC to 3u) g of preveighed silica gol from Its
container to the fourth Ixnpinger. More silica gel may b*
us*d. but tart should b* takfcn to ensure that it is not
eutrathe sampling train has be«n assembled, tnro on
and set th* dlur and probo heating systems at thtdeaind
operating temperatura. Allow dm* for th* temperature*
to stabiiitt. If a V iton A 0-iing or other leak-tree connec-
tion is used in assembling tb* prob* nocti* to the prob*
liner, leak-check tbe train at tb* sampling sit* by ptug-
guag th* notzl* and pullicg a 380 mm Hg ui in- H*J
vacuum.
NOT*.—A lower vacuum may b* used.. ?raTid»d that
It is not exceeded during th* test.
If an asbesto* string is used, do cot connect th* prob*
to th* train during th* lemkakag*
rates in excess of 4 percent of the arerag* sampling rat*
or O.CTXU7 m',min (0.02 cto), whichever is less, ar*
uxtaixeptabl*.
The lo(lowing leak-check Instructions for tb* sampling;
train described in APTD-M76 and APTD-05B1 may b*.
helpful. Start the pump with bypass vale* fully open
and coarse ad)ust valve completely closed. Partially
open tbe coarse adjust valve and slowly clos* tb* by?*>a
valve until tbe desired vacuum is reached. Do not revers*
direction of bypass valve,; this will cause water to back
up into tfaa filter holder. If th* desired vacuum is ex-
ceeded, either leak-check at this higher vacuum or end
the leak check as shown below and start over.
When tbe leak-check is completed, first slowly remove
the plug from the inlet to toe prob*. filter holder, or
cyclone (if applicable) and immediately turn oil th*
vaccum pump. This prevents th* water in the impingers
from being forced backward into the niter holder and
silica gel from .being entrained backward luto the third
impinger.
4.1.4.2 Leak-Checks During Sample Run. Tf. during
tt* sampling run, a compon«nt (a.g.. filter a&aejcbly
or Impinger) change becomes necessary, a leak-check
shall be conducted immediately before the change is
mad*. Tbe leak-check shall b* dom according to the
procedure outlined in Section 4.1.4.1 abov*. except that
It shall b* done at a vacuum equal to or greater than th*
muuniizj value recorded np to that point in tbe test.
If the leakage rate is found to be no greater than O.OXrS?
m'/min (0.02 cfm) or 4 percent of th* average sampling
rate (whichever is less), th* results are acceptable, aad
no correction will need to be applied to th* total volume
of dry gas metered: if, however, a higher leakage rat*,
is obtained, the tester shall either record the iwkag*
rate and plan ro correct tb* sample volurc* as suown in
Section 0.3 of this method, or shall void th* sampling
run.
Immediately after component changes, leak-checks
are optional: if such leak-checks an done, the procedure
outlined in Section 4.1.4.1 above shall be used.
4.1.4.3 Tost-int Leak-Check. A leik-checL Is nanda-
tory at thf conclusion of each sampling run. The Irak-
chock shall h» don* in accordance «"ith Uie procedures
outlined In Section 4.1.4.1. eicept that It ;haU be con-
ducted at a vacuum «tual to or ^renter than th* ntail-
mum value rcorhrd durinn tlie sampling ntn. If th*
leakage rate is found to t» no gieater thinO.000.i7 rnVmin
(O.ff-' cfm) or 4 prrcent ot the arena* sampuue rat*
(whichever Is le&j,', the results are acceptable, and no
correction need b» applied to th« total vulum» of dry IKS
metered. If, however, a higher leuk»for*
and s.'ur i ,u:h leii check, nud vh«n sumplu>£ 13 tuviusL
FEDtXAl
iS, VOl. 43, NO. 160 — 7HUS5DAY, AUGUST 18, 1977
-------
RUlsS AND REGULATIONS
•ui 3li*r mdlnn rtotititd by Tlfon &-2 at \aat aan
^.•b mnpl* point auriiu «cli am* menntBi u>d
Vina*! mdlao *h»a 3iiaifi-
•ul >U)iuan«au in flo« nte. Le»«l sad ure UM
auo:ii«ur. Bteniu* lh* maaoauur l»»el and tero raty
tli du< WT\br»uoa< autl umpcraau* ouo(<*, ra»i«
.-•ciUc "j*--Jtj dunot Uia tnvcn*.
Clean th* porthoUi ortor ta UM tart ran M minimi**
UM ch*Do» of aoicHiat daootlud maunalL Tn bap*
sampling, runat* UM nouM cap, T*nty Uuu a>« filur
and yrob* Oman* ryiuau an ut> ta tampwaair*. acd
that UM pitoi tutM and prob* an prepmy pcniuoiMd.
PojiUoo tb* ooule at ta* arr. invent pouu v.vb in* op
poinuag du*cUy u»o UM cat nream. T*n~,»itimiiy surt
UM pomp tad adlon to* flow ta tsotln«ac ooodiaocu.
NomotTtfiat ar* arauabk, vbien aid la UM rapid adlow
w
eoxapaaaom. Tfi»* noauwtu *r» iWunmi lor »•
W*MU UM Trp» 9 piy tnb» oxffieitai U IU&±KU&. and
•JM tucx nJ xrolrvtuu density (dr» mowotar wvtat)
I* aqaal ta •:»=*. i.PTD-0678 dauui* UM oroo*"tar« lor
T-«!3j th* noiaocrapra. II Ci tad i/j an maid* Uv*
v-«J»« stated raa**> da nat ost UM cnmotnoO oaioo
appropnwa reap* (*•• Citation 7 tn S*e;ua 7) an u*aa
u eoiop«n«»i« lor UM d4HMlaov
LOCATION
n?E«ATOR
BATE
RUN NO..
SAMPLE BOX HO..
METES BOX N0._
MSTEBAH9
C FACTOR
AMSIEST TEMPERATURE.
BAROMETRIC PRESSURE.
ASSUMED MOISTURE. X _
FROtElENCTH.adl) .
•NOI21E lp£«TIPlCAT10n "n
AVERAGE CALI1RATEO NOZZLE DIAMETER, i
PITOTTU3E COEFFICIENT, t,.
SCHEMATIC Of STACK CKOSS SECTION
LEAK RATE. »3/«-.(rfa)
PROBE UNER MATERIAL
STATIC PRESSURE, aa HIG*. H|j.
FILTER 1"
TRAVERSc POI^^T
. N1JMS£H
TOTAU
SAMPLING
IIMi
(<1. mill.
AVERAGc
VACUUM'
""H^
STAC*
TEUKKATUKt
ITS)
•ci«n
. •
VELOCITY
HEAD
(A?s).
mCB.lMjO
P*£5SURE
OlfFERfNIIAL
ACROSS
ORiriCS
UETU
nnUjO
(tn. HjOl
OASSAMPU
VOLUME
i"3 (ltJ»
A
«
GAS SAW*»a TEMTOUrUtt
AT on GAS weni
INLEl
•c rn
OUTLST
*C (*F1
.
1
Av^.
A»9.
A«». . .
FILTEJI HOU3EX
TEWtMTUICC.
•c(»n
Tamunjitt
' OF GAS '
LEAVING
CONceezs oa
IAST iwi»ca.
•C(f)
th« jtaclc b under sutrofi-.-i
t o! ncpuntr :v«3j'i, UJu c&:« ta close tb< coan*
r«rtini iSo prab« into tt» TUct v>
PUT*IT. vaut Iron bxrtiU i^ta tbo Slur holdw. U
ni^— ss»ry. tho pump aiy b* tumed oa irtUi th« cc«n*
u-Ijrjt T»IT» doe«d.
Whoa tb« pmb« is la posittaa. block aS th« o'xninti
^rcur.d til* prob« 5nd portholv Xo prtveai unrtpr*-
s«nt*tiT* dllntlun of the zu str^acn. •
Tntr«tilul not
to b'lmp ttt prub* until* Into th» suck wtlli vtita
vtmplin; np»r th« ralb or trbrn rtaonni or u-j«mri
tiit [>rob* iLrr:i'n tt« rrr.tnu ta
k-ip t*i» '*mp«mtur* troimd tlw IUt«r boidtc »t tti*
prni>«r ItreU »dd mor* 1ft and. U nfC«tui>t uotbtr conpUl* Oltw UMtcblr
\-< "<"d rather thin iltempunj to chxnzt lot Uter itMll.
. ,
»wt (*» Section 4.1 4.2). Th« tottl p«rUcuj3t» wjgj
itiMl . Mi-ludc tb> siiramitiOQ of ill alter kwmbly »uh->.
.v «'.ngl« train 'RiUl b« und for the eatire umpl* rue.
tn »pt In CUM »-h*r» sL-ialUowu laopUr j a rmulred
in two or u»-" ii r;»r»w du"ts ir at two or rr''f< di;.'erent
n wo or u»-" ii r;»r» u"s ir a wo or rr''f< ;.eren
!.•>• \> rtnj w:l!\iH the saoi* duct, or, in coses where cquip-
it.fci.C'f'».l:ir« oocwi'Jitu a c^in{9 of tr«irs. In all otbcr
sitnnnoiv tn« TI..< o( tvro or more truni will b< aubj^t to
.h- •ippctiv*. j; ;U» .vlaiiijtnto:.
- Figure 5-2. Part'.culata field data.
Xote that irfa«n two or mor* tralnj an owd, Mpant*
analyiM of tb* Iraac-ball and (U sppUdbU) Imptniw
catcbeg trotn acb train sball b« porlorcicd. unltu ideca-
csl aoide slu> vere OMd oa ail tnlni. in voicb CAM. va«
front-ball cattbtt (ram th* Lndindml truna may b»
cambuicd (\s icay tha taptnger eatcbas 1 aod pot ia»iriJ
o( Iront-hAl! catcb aad on* acalysti o( Lapingu catcb
m»7 b* pcrforatd. Coosnlt wHb tb* Adsuninratot tor
detalU conwnung tb* calculsUoa o( rwulu vb*a tiro or
moro traini an us*d.
At tb* end o( tb* wmpl* nin, ton off tht eoane adl'ut
T«lr*. riooT* tb* prob* and nottl* Lisra tbt suet, cum
oil th* pump, nrord th* final dry ju zi*t«r r>a>ling, and
coaduct a po«-u»t Iwik-cbtct. u outlined In SKI: on
4.1.4.1. AIM. leak-check th« pilot Usu u Otvrtb«d in
MeUiod 2. Section 3 I: th* Unu tctut ru> tali l**Jc-:b^.t,
In order ta ralldat* tb* v«locuy bead dsu.
4.1.8 Calculation of Percent Uotar.'tic. C»lail»u
p«rr*at bokuuttc (w« C»lcula:lou, Section ») ta diui-
nune whether tb* nin v&s ralid or another ten nin
ibould b* mad*. II tbtr* vu djnrolty in m&intairurf
iMldn-clc ratu due to jource coacUtmns. coniult »".-.b
tb* f JJm]niy-r*tnf for pOUiblv TarikOC* CO tb* iSO^UltClC
ntu.
4.2 Si*mp\e Hecofery. Proper cleanup proce*1ure
br?iru u soon u the prob* Is remotj'd (rasa the succ »t
ih» end Of the sampling period. Allow the prab« to cool.
When th* probe can be ulely h^dltd. wip« o2 ill
etumol partlcolate matter near tbt tip of toe prob*
notilc and place u cap ov»r it to preveot Icnin* or ga;^r,j
particulate matter. t>o not cap o3 tbe probe tip Uglily
whilt'the sampllai train D cooiia? clo^- u thu woull
create a Tacuiiin In the filler hoU»r. thus dravnnt va-^r
torn ti» imrur.f en imo th« fU:«r holi?r.
•Uetore movma ihe sampla train -,o l!.e c!-»nup «'/»,
rcmoTt ih< prnL>« from itie sa:iii-l> ;r»ir.. »nj>? o- ''.*
ere&». and cap the open oaU*t at tbe pnb*. B»
not to low &ny eoadenjate that ml9h: D* preaecib
d the rdiccno ftta» from tie (Uur inlet vber* tb*
probe wu !i3MDeton* bllut."
Iasp«:t ine train prior to and dutlnr dUaswiablT and
-ote ar.f aicoraji coudluoos. T.-v«i th* vunpld ill
.
Cw.'i — -V». /. Caretully remove tn» Mtir from th»
liter ho'.'^r »nd plac* It In itj Mcntiaid pstri disa con-
tainer. V-* i pair of twwzers and or clean dispojibl*
«u."pc»l I'.ores to handle th* Alter. U It b necessary to
fold •..** i:'??. do so 5u:b that the paracuiite cite la
laslde tat fold. CareJ'illy trans!er to the r*:rt diib, any
part-;a~i:e mistier andjor liter fih«— »-'jicn adaere to
the ."J'.v bolder «isl;e:, by ados a dry nyloK briAU
bnu1! ir.>l ;r a s'jitp-ed?sd bUde. Seal thecont»ia«r.
Cii'J.^.-— ,Vo. t. Tatinit e»re to M« this dust oa ui«
outs'..!* ol :'yt probe or other citertot surtK** dan* not
;-:t ir.to t=« N»--=i>;-\ cUACtltatiTely roroT«r p«rUcui»«
=.\::»r o: .>: y cond»iuute Irotn tU* pro'j* a*ti«, prol»
FEDESAl. RECIZTES, VOL. 43, NO. 160—THURSDAY, AUSL'ST 13, 1977
-------
417SO
RULES ANt> REGULATIONS
fitcna. prob* lintt, and frmn
j«* oomcra'B*iiby tbg
b* o»d. wtun. »5beifl«i fcy tho
oi Uta Uliaf boiiitr by
ceUbrmaart placing O«
y b«* Q4*d
Rant.
dlxactiooj oo.
.
Cart-folly rtrmovo the proas
rurfaro uy ncmng witii icrio
tjrujo:r.(t witfl a nrloo bru'
rxr--nn« rtiuo shows r.o r-^
u^-rtnw of U» Baffl*
anti rtcaa the iosi
luL-ur viUL acauw* In a
Pdarm u
c^k Md cJraa Ui« load*
e fmr.i a wtub boute and
urubli. Bruao until tb*
le paru^Iai, aitai wtmifc
s-ortaer with acrtone.
parts of Uia.
way mrtQ no-
. .
fnia* the pr>H-> brv-^ wuh &«WHW by
rounnz the pro'w wlule ^mlnln* ac^rma into its upp«
pud so thai all tnsxl-r "urracrs will f» -wetted vlTft a*
wunpt^ rrtntpJnfr. A frrmi^i (^ara or pol7>?thTl|'fl*) may
Ui Oicd 10 a*d In traaiitmas aqoiti %u*ii«o to LO« con-
MJii-»r. FtHlcrw iho bcf^trtw nrrap? wltFi ft pn>L>« bmah.
IJoid th» prob« in an mclin^ p<>iiineu aqiurt acewo*
intn ti« trppT end aa tV pmri* braan u twic^ pasii«l
>t Uh Q r viiiui^ icooa tiiTjUtin tliu prol***: hoed. & •MJBpi*
cooLAjO'-r andern»aLii Uie io*-sr ••Mfl o( iA6 prob*. and
men &ny a*
iui ict^fj*i^, aud f|iuiorti
ihfl flHEDpI* cooiaintT. A/Ti-r *J)« orc?hrrdt. mate a
uul iv-«iood nose of iho prot_*j> aa [i It Is sblpp*d to tiio laborato-rr. Wwfc U»
h**iffht of tbe Ould IBTCJ to deterniLna •wbethcf or ixH
Iftiicags octurrwl during transput Lalwl Lb« ctjnt&m«r
to clearly Identify its ronttriu.
Contcinfr l\'o. 3. Note ibe color oftbc indJcatJnjt sQTc1*
5«i to fletaisrujia Jit hM beta rcmpwtely sp^ncand rafc^A
a notation of lu condiQTn, TntQi^f Uit- slLtca gnl tram
ti« fourth Lmpmiir to ILS ontuwU cont&ixurr ajid »e«J.
A funnel may ma^a 1 1 eamer to potir Lbesilira JTB! without
sudlinz. J. rubber polu-auiw* iray tm LLt*sd EJ an &ija nnalysu of LQe Lmpjngtr catcJS
LI r«aiu'»-J is«9 Note, Src^on i.1.7).
U" a diiTtfirnt typo of cociJ^Ti^'' la a."*f For purpows of
t-'ii« Secu&n. 4 3, Ule t«m "coortaui; wptght" meaca a
0 jitTpnc* or nu tnoro thin 0 i og or 1 p*irc*nt of u>LaJ
>*8ifbt leu uu-f »riEht, wbjch^Ter ts 8TP4t*r. txtwwn
tvo cin?js:uU»« •»1nJihLT.Sa, w;tb no l*ifl tbJU) C tour? o/
Run Na._
Filter No..
. Amount liquid lost during transport
Acstone blank volume, ml
Acetone wash volume, mi
Acetone blank concsntration, mg/mg (equation 5-4).
Acetone wash blank, rng (equation 5-5)
CONTAINER
NUMBER
1
2
TOTAL
WEIGHT OF PARTICULATE COLLECTED,
mg
RNAL WEIGHT
I^^^^CL
TARE WEIGHT
I^xC^
Less acetone blank
Weight of paniculate matter
WEIGHT GAIN
-
.- -
-
FINAL
INITIAL
LIQUID COLLECTED
TOTAL VOLUME COLLECTED
VOLUME OF LIQUID
WATER COLLECTED
IMPINGER
VOLUME,
ml.
SILICA GEL
WEIGHT,
&
g* ml
* CONVERT WEIGHT OF WATER TO VOLUME BY DIVIDING TOTAL WEIGHT
INCREASE BY DENSITY Of WATER (1g/ml);
3 - VOLUME WATER, ml
1 g/ml
Figure 5-3. Analytical data.
FLD:FLAI UGISTJ*. vcu «, NO. 140—-THURSDAY, AUGUST is, 1977
-------
r. the sarcpl* nuy b*.OT«i dri«3 at 105" C
K) for 1 to S hours, cooli-il in th* diMiccftior. and
wi to A COILS taut w*>tKhc. u/vi^ a otb«rwu« sp»9cLfi<*l
by tna \dmmLStraxor. The KAC*K m&y aiio opt to ovta
rtl-y thoflampleat 106 * C (.20* F) lor 2 to 3 boon, weisn
*h> itunpM, n-nd UM thii w«iio or
, subject co tfle approvftl of tha Admuusx
10 cumc- ta« final r caul Li. Me*Auro tho liquid in
contain w fitb^r TolumBOlcaUy to ^1 ml ox jt
metrKaltT to iO-i g. Tranaier the cont«au to t
,150-ml txalcer and ev»porai* to drrneja at anibt«at
t«nip€r»cu.™ and presiurB. 0(*atccsi« for ?l boors aad
weijti ta a con*t,uit wet^bL Beport the renlu to tb«
QMrest 0.1 mi.
Ciinfam.rr Ao. J. Weigh the 3p»at siliefl R«l Cor silica RO!
plus Lmpmcw) to tb« aev»xA 0^ e tuuig & btUnca. Tbu
nap may be coodLictKl 10 c&« fctd.
"Aaton* £i&nk" Con/aiTur. Measuro acetone la tbij
eitber YoLumaciiaiUy
Tnru/M the acctoae Co A tar«d 2.VWnU be*ka.r BJQC!
onte to drynM* at ambient Lamp*f»turc and pr«»ssar»,
PealccttA tor 24 boon and we*.^ to a coau&at wetjttjt,
Report tha rsauiu to tbe ortn-st 0.1 mj.
NOTIL— At tha option o( the uatAr, tho coaUaU of
CaaUinw No. 2 as w«Q tu tna ac*tc>Ge bLaafc
'may b* »raporat**d, ax unip«r*tur«9 higher
eot- II er&pontn>n 'a doa« at an ei«tVB>d tJ
the ump«r^cun* Li oat b« b«lo*r tbe boiiin^ point o( tbe
»l»ent' also, to praroat "bumping," tbe evaporation
procasa miiat b*« closely iupcrTL3*d. and the COQU^QU of
the b«itw muat bf» T^i/t-a occajionaJly to ouantAui an
temperature, tJsn tfrtrecid Ci*re, as acetona u highly
jas ^ low g*-?>i petal.
Atan ft kooratorr loff oi oil ealibratioai.
i.l Piob* Nosile. Prob-e ao«il»rj sti&U b« calibrated
be/ora their iiutial UM in tii* ftcld. Uainc a micrometar,
he irmde diameter of the nozzle to the near«di
RULES AND REGULATIONS
0.02! nun id. 001 la. ). Make three separate
using dUerent diameters each Urue, and obtain in* a»er-
a«e o< the meefur&annu. Til* dulereace between th« h.^n
and loir numbers iball not exceed 0.1 mm (O.IXM in.).
Wbea noiil«t become nicked. dtoced. c« temperaturt
tcnjJXea. Dial trlennometen. suca u &r» ua«Ki Cor tae dry
£01 oitur tod condeoj«r oullrt. itaU be cm!K>r»(*d
airaitsc ourmry-irr-glaji ib»rmnm«i«n.
^A LxKji Cbto^ o4 ^Ittrrinti drnem Saovn In r*1cnrt
i-l. Tow porQoo o( th« «mplin« train Iram the pump
u>ib«ortUee mtur ihould twl«k cnecimci nnor loinidal
uvundUHreacb jfupment- Ui»X»«» altrr lb» pomo \«1U
nsuii in !•« Tolucit h«n« m-orrlfd LUan Is aoniAlly
sampled. Tbe. [otlo«rtnn proonlurr U m »A *• •" I *>*•
F^rur* A— I): Close the main T^l»t on ifi* ci«l«r boi.
Invrt » oa*-oolt mbb^r not>p*r with rub&er tub»n«
afljchnd Into the ortdc* txbaujt pipe. OLKoaoeca and
Tern tb* low ttdt OJ lae orlGoa rn*aom« L4 am
(5 to 7 Ln.) vmur oolnmn by blowing luto the rubber
tnbinx. Pinch ofl tht tuOtag and nhtem ( tie ouaaoaituer
Cor oat minuta. A lota of presort on the omaomtttr
Indlc^xn » Inil: In tbt cn««^r boL: k»ri. Lf pramL. muA
be oorr>-ct*d.
5.7 Baroomer. Calltxrue K»UL«. a mercury berom-
8. Caieaiatioru
Carry ocrt rajcalalioal. retalniiat at le«5t ooe em
decimal a^ura btyocul toai oV tb« aoqulr^i dafa Bound
on nirura after tbt ftnul oiJ»"
component changt (^Ml, X 3 .... n)(
m'/min (cfm).
-Leakaeo rate obserrwl during thi post -test
leak check, nj,'mln (ctm).
""TotiXi amount of paniculAte ms'tercoutxitfra,
-Molecular weight of water, 15.0 fnj-tnoU
(13.0 lb/lb-mol«).
—Maw of residue of acetone aft»r araporatioo,
.
-Boron«trle prw>ur9 at t'
nun Hn (In. Eg). . _
-Abiolute stable iMprtasuro. mm H? (in. Hir>.
-3ur.-L--d absoluio prn<5ure, 760 am Hj
(•-•<.« in. Eg).
T.
-Ideal gas constant, 0.062M mm Hg-mVE-g-
mole (21.M in. Hg-«V°R-lb-mole).
-Absolut* average, dry ras meter umperatnre
(see Figure S-J), "K ("ft).
T, -Absolute areng^stack gas temperature (see
T,u -Standard ab»tat» temperature, 233* E
(52S' E).
V« —Volume of acetone blank, mL
V,, -Volume o( acetone used In wa»h. mL
Vu —Total volume of liquid collected in impingers
»nd silica gel (j*e Figure 4-3). ml.
Ym" Volume o( ;u sample as measured by dry ga*
met«r, dcm (dd).
V.(.«i-Voluin« of gas sample measured by the dry
gas meter, corrected to standard conckdou,
dscm (dsc/).
V.(..4)-Volunie of irster vapor In the gu jampla,
corrected to standard condition*, scm isc/].
V.-Stack gas Telocity, calculated by Method t.
Equation 2-9, using data, obtained from
Method 4, m.'ste (ts/sec).
I^.-Weigbt of resldut in acetone w»ah. mj.
y-Dry gas meter caiibracioe factor.
AH-A«ra?» pressure- differential across tbe orinr«
meter ue* F'urur* 4-2), oa HjO (in. HrO).
• ,-Deusity o( acetone, mg/ml (see label on
bottle).
/.-Detuny o.' waier. O.WS2 t'ml (0.0,^201
Ib/ml).
1 = Total sarcpling tisie. min.
' I: " Samplin< tim« interral, from e ttnnnt
at a run until tht OTA component cnacga,
Tnln
w time Laurrmi, b«rw*cn rw« suc-
cefclive component ci*-an$eA, t>e?Lru3inc with
th« interral between the tm and second
changea. nuxu
1,-SampUnt tLma tnterrj, turn th« final (n^t
component caarijrs until the tnd oi tbe
sampling run, min.
115»3p»ciac gravity at mercury.
G0"»3ec/min-
100— ConTenion to percent.
6J ATlraia dry gai Eeter temperature and
or!2c« preaaure drop. See daiA sheet (Figure 5-2).
6J Dry Gas Vo'.umt. Correct the sajnple roliicit
measured by tb» dry f« meiw to standard conditions
CO* C, 760 Tnm Hg or W f , 29.92 in. Hj) by
Equation
13.6
P..
i-i
FEDERAL RECISTE», VOL. 42, NO. 160—THURSDAY, AUGUST 13, 1977
-------
RULES AND REGULATIONS
mi— 0 JSAfl •
- 17.M '
H« .'or m^rtc L Ko mrapooeot cnann* maj«
a*mplinc ran. In tnu c**«, repUc« ^ « In Equation
vita tbe expression;
NOT*.— ti
itnama. two
Maraud
or walar dreplet4»d«n t»»
of lb» mautun <-nouat a< UK
« nra*i*w one Lmn t
&rt4 * Mcor.d Crom to*
mmtioooi. Tr» io»-«- ca to*
i t>* rrmjiderpd carrot. Tb% pracedar* (w d*t«i.
tii t7 oixtun ooatdat httd««l uoon cmnmpuoa oi
U n««c tn Cu Nnu o( »>moa U
olM* purpowa oC Uiu aKtbod. U)«ir«rM>
rapwmcure trom Firm V?
. prondMj tfr«c
lh« ui-ftac* umpvmcun Haior LI ± i* C U" FV
6.6 Ac«lon« BUJix Coacuttnuoc.
fb) Cat* U. Cm« or man eompaaut rn«nn>»
dnnmr tb« «rnplmr nm. la Uu* ca». replace
and 5UbnhUt« only lor thoae
vnica nosed L.
6.i Talma* a/ vatrtr -raoor.
rat« (I, or L,)
—0.001333 nj*/rni Jor in«tr!e urttt
-O.CM7D7 rt«rnJ lor Enilnh uiutl.
MoLjtnn Conunt.
B,.=
V St
• P.
(.7 Actuxw Wa«h DUnl
IF.-C.V../,.
«J Total Particniate TTeltht. Detarmin* Ou
torn oonuiaan 1 »nd 2 \em the ar«mn« bbuik IM« 1
S-JL Nor».—R»iar to 8*cGon <_] J u again la calculation
of mula LnTorniu two or mon Hur aaembliM of two
or mom sampling cr&uu.
^ 6^ ParocuMu CooomtratlaB.
6.10
To
UalUpl7 by
t:lij
sift'
!b/n»
«0a V»rl»don.
&.11J Calculi rtno From R»w
A',-O.COMS< mm ns-mVml-'K tor oelrlc onJta.
-O.OO^aa in. H»-(t'ttnJ-'R lor Eojjlish onlu.
8-1LJ Calculation
T.V.
8.13
n i— 1 Vft tor m«tru onit3
-CLli-tiO lor Entliib muU.
13 Ao«pUbl« RtMitta. LI 50 p«re«nt
abl« raog«, or, U I iJ le^s tb&a 90 percent, tb« AHTnmi*.
trator may opt to accept ta« rr^uiix CM Citation i to
matajcdgaiAnLs. Otafnri», reject tb« reaultj and r*p«at
Mitten.
1. Addendum to Sp Tnad(J*
Park, N.C. .N'oFtovtxr. 1076 (unpubliined p«par>.
9. tr.nn.i Boot of AjTM St&ndvdj. Part 24. Ouoona
Fii^li; Coai and Cokt; Atmovpharid Aoalysia, Aja«rtcui
Sociicy tor TuOni aod '"-'IT'I FhiUddlptua, Pa.
l»7t pp. «17-522.
METHOD
Tiox or Sinrcx
FEOM STATIONABT
DIOTTPE
L Prtntiflt and .-tppleaiSUf
1.1 PrlnripU. A r»J »apU li eitrsctod Irom li»
nmpllnf point IB tn« stack. To* suUucc acid mm
Cincludint suirof crioxldf) and tb« soirar dioijd* ar*
i«pa.-«t4KL To* mltor dioiidt Inc^oO J measured by
tb« bantua-taorta Utr&^on meUuxk
U AppUcabiilty. Tnii method la applicable for Uu
determination of stiUur dlnilde emiuioos trom stationary
K.UTCM. The tnintT-inm datecublt limit ol tb« icetnod
nu b««n drtermined lo b4 3.4 milligr&cu IIEZ' of SOt'm1
(112X10-' Ib'ft '). AJtboosh no upper limit baj bMn
utabliibtd. tedU DST« sbow-n tbat eoncmtnuoci u
bigb u 80,000 mtin' ol 60i can be coVlecwd efficiently
In two nudset Lmpin^tn, escb concainlng 15 miiii!it*r?
o( 3 ptrwnt" aydroien p«roi;de, at a r»i» of 1.0 1pm lor
20 minoto. Baaed on ibeorettcaJ calcoiaUou, tb« uppnr
conc*atruion limit In a 2>htei £unpl« li about 93.3CQ
.
Poasibl* !irUr>r«ots are fr*» aimxotia. w«ter-«X)hjbU
eatlotu, and naoridd. Tb« cauotu and fioortdM ar»
remoTed by jlaaj wool tilers and an uopror»ool bobbin-.
and hetc.e doom aSect tb« 3Oi analyst*, vfbeo nmpka
art beiot taLen trom a tu su<«m vitb M{b cooc« (fuci as tn Inleta to
eonrrcl d«Ti«s), e hi?n-«aiclencT glasa tb*r ftlt«r man
be ued in pitt«-o( tbe !ii;-5 wool plug (I.e., tnt oo* in
tb* prot1*' to remoTt the cation inwrferentj.
Fre« srmonia interlero by re««!j:| »1th SOi to form
purticuiau solflte and by reacting wttn tbe indicator:
If Im ammonia H pr«Mnt (tnia can b* deterrr.inwl br
tnowledfe of tn« proo=» and noicku; whiu panlcui*t4
matiB rn tn« prob* and ljoprop»nol babbler), aluroo-
CT« methods. rab)«ct to tbe approi&l of tbc Aflm'Tintrm-
tor, XJ.B. Enrlronmtr.tal ProttK.tioi> AjencT, art
nqolrod.
FEDERAL 8EGISTH, VOL 42, NO. 160—THUBSDAY, AUGUST 18, 1977
-------
Attachment E
Determination of Total Polychlorinated Biphenyl (PCS)
Emissions from Industrial, Sewage Sludge, and Municipal
Refuse Incinerators (Draft Method)
-------
PART A. INDUSTRIAL. SEWAGE SLUDGE. AND
MUNICIPAL REFUSE INCINERATORS
1. Principle and Applicability
1.1 Principle. Gaseous and particulate PCBs are withdrawn isokiaet-
ically from the source using a sampling train. The PCBs are collected in
the Florisil adsorbent tube and in the impingers in front of the adsorbent.
The total PCBs in the train are determined by perchlorination to decachloro-
biphenyl (DC3) and gas chromatographic determination of the DCS.
1.2 Applicability. This method is applicable for the determination
of PCB emissions (both vaporous and particulate) from industrial, sewage
sludge, and municipal refuse incinerators.
2. Range and Sensitivity
The range of the analytical method may be expanded considerably
through concentration and/or dilution. The total method sensitivity is also
highly dependent on the volume of gases sampled. However, the sensitivity of
the total method as described here is about 10 ng DCS for each analytical
replicate.
3. Interferences
Excessive quantities of acid-resistant organics may cause signifi-
cant interferences obscuring the analysis of DCS in the perchlorinated ex-
tracts. Biphenyl, although unlikely to be present in-samples from combus-
tion sources, can form DCS in the perchlorination processes.
Throughout all stages of sample handling and analysis, care should
be taken to avoid contact of samples and extracts with synthetic organic
materials other than TFE® (polytetrafluoroethylene). Adhesives must not be
used to hold TFE® liners on lids, and lubricating and sealing greases must
not be used on any sample exposed portions of the sampling train.
4. Precision and Accuracy
From sampling with identical and paired sampling trains, the pre-
cision of the method has been determined to be 10 to 15Z of the PCB concentra
tion measured. Recovery efficiencies on source samples spiked with PCB com-
pounds ranged from 85 to 95Ti.
52
-------
5. Apparatus
5.1 Sampling Train. See Figure A-l; a series of four impingers with a
solid adsorbent trap between the third and fourth impingers. The train may
be constructed by adaptation from a Method 5 train. Descriptions of the
train components are contained in the following subsections.
5.1.1 Probe nozzle—Stainless steel (316) with sharp, tapered
leading edge. The angle of taper shall be £ 30 degrees and the taper shall
be on the outside to preserve a constant internal diameter. The probe noz-
zle shall be of the button-hook or elbow design, unless otherwise specified
by the Administrator. The wall thickness of the nozzle shall be less than
or equal to that of 20 gauge tubing, i.e., 0.165 cm (0.065 in.) and the dis-
tance from the tip of the nozzle to the first bend or point of disturbance
shall be at least two times the outside nozzle diameter. The nozzle shall
be constructed from seamless stainless steel tubing. Other configurations
and construction material may be used with approval from the Administrator.
5.1.2 Probe liner--Borosilicate or quartz glass equipped with a
connecting fitting that is capable of forming a leak-free, vacuum tight con-
nection without sealing greases; such as Kontes Glass Company "0" ring spher-
ical ground ball joints (model K-671300) or University Research Glassware SVL
teflon screw fittings.
A stainless steel (316) or water-cooled probe nay be used for sam-
pling high temperature gases with approval from the Administrator. A probe
heating system may be used to prevent moisture condensation in the probe.
5.1.3 Pitot tube--Type S, or equivalent, attached to probe to
allow constant monitoring of the stack gas velocity. The face openings of
the pitot tube and the probe nozzle shall be adjacent and parallel to each
other but not necessarily on the same plane, during sampling. The free
space between the nozzle and pitot tube shall be at least 1.9 cm (0.75 in.).
The free space shall be set based on a 1.3 cm (0.5 in.) ID nozzle, which is
the largest size nozzle used.
The pitot tube must also meet the criteria specified in Method 2
and be calibrated according to the procedure in the calibration section of
that method.
5.1.4 Differential pressure gauge—Inclined manometer capable of
measuring velocity head to within 10% of the minimum measured value. Below
a differential pressure of 1.3 mm (0.05 in.) water gauge, micromanoneters
with sensitivities of 0.013 mm (0.0005 in.) should be used. However,
53
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Stack
Wall
Thermometer
Florlsil Tube
Probe
Reverie-Type"
Pitot Tube
Manometer
Control Box
Figure A-l._ PCS Sampling Train for Incinerators
54
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micromanometers are not easily adaptable to field conditions and are not
easy to use with pulsating flow. Thus, other methods or devices acceptable
to the Administrator may be used when conditions warrant.
5.1.5 Impingers—Four impingers with connecting fittings able to
form leak-free, vacuum tight seals without sealant greases when connected to-
gether as shown in Figure A-l. The first and second impingers are of the
Greenburg-Smith design. The final two impingers are of the Greenburg-Sraith
design modified by replacing the tip with a 1.3 cm (1/2 in.) ID glass tube
extending to 1.3 cm (1/2 in.) from the bottom of the flask.
5.1.6 Solid adsorbent tube — Glass with connecting fittings able to
form leak-free, vacuum tight seals without sealant greases (Figure A-2). Ex-
clusive of connectors, the tube has a 2.2 cm inner diameter, is at least 10 cm
long, and has four deep indentations on the inlet end to aid in retaining the
adsorbent. Ground glass caps (or equivalent) must be provided to seal the
adsorbent-filled tube both prior to and following sampling.
5.1.7 Metering system--Vacuum gauge, leak-free pump, thermometers
capable of measuring temperature to within 3CC (~ 5°F) , dry gas meter with
27» accuracy at the required sampling rate, and related equipment, or equiv-
alent, as required to maintain an isokinetic sampling rate and to determine
sample volume. When the metering system is used in conjunction with a pitot
tube, the system shall enable checks of isokinetic rates.
5.1.8 Barometer--Mercury, aneroid, or other barometers capable
of measuring atmospheric pressure to within 2.5 mm Hg (0.1 in. Hg). In many
cases, the barometric reading may be obtained from a nearby weather bureau
station, in which case the station value shall be requested and an adjust-
ment for elevation differences shall be applied at a rate of -2.5 mm Hg
(0.1 in. Hg) per 30 m (100 ft) elevation increase.
5.2 Sample Recovery
5.2.1 Ground glass caps—To cap off adsorbent tube and the other
sample exposed portions of the train.
5.2.2 Teflon FEF® wash bottle—Two, 500 ml, Nalgene No. 0023A59
or equivalent.
5.2.3 Sample storage containers—Glass bottles, 1 liter, with
TFE®-lined screw caps.
5.2.4 Balance—Triple beam, Ohaus Model 7505 or equivalent.
5.2.5 Aluminum foil—Heavy duty.
55
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10cm
if A
\
\
\
\_, ^
\
\ .*-
A
\
\
\
r
\ ^~s
r
i
2.5cm O.D
2.2cm l.D.
j 28/12
Figure A-2. Florisil Adsorbent Tube
56
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5.2.6 Metal can—To recover used silica gel.
5.3 Analysis
5.3.1 Glass Soxhlet extractors—40 nm ID complete with 45/50
-------
5.3.19 Porcelain casserole—Capable of withstanding temperatures
as high as 650°C.
6. Reagents
6.1 Sampling
6.1.1 Florisil—Floridin Co., 30/60 mesh, Grade A. The Florisil
is cleaned by 8 hr Soxhlet extraction with hexane and then by drying for
8 hr in an oven at 110°C and is activated by heating to 650°C for 2 hr (not
to exceed 3 hr) in a muffle furnace. After allowing to cool to near 110°C
transfer the clean, active Florisil to a clean, hexane-washed glass jar and
seal with a TFE^-lined lid. The Florisil should be stored at 110°C until
taken to the field for use. Florisil that has been stored more than 1 month
must be reactivated before use.
6.1.2 Glass wool—Cleaned by thorough rinsing with hexane, dried
in a 110° C oven, and stored in a hexane-washed glass jar with TFE@-lined
screw cap.
6.1.3 Water--Deionized, then glass-distilled, and stored in hexane-
rinsed glass containers with TFE®-lined screw caps.
6.1.4 Silica gel--Indicating type, 6-16 mesh. If previously used,
dry at 175°C for 2 hr. New silica gel may be used as received.
6.1.5 Crushed ice.
6.2 Sample Recovery
6.2.1 Acetone—Pesticide quality, Burdick and Jackson "Distilled
in Glass" or equivalent, stored in original containers and used as received.
6.2.2 Hexane—Pesticide quality, Burdick and Jackson "Distilled
in Glass" or equivalent, stored in original containers and used as received.
6.3 Analysis
6.3.1 Hexane—Pesticide quality, Burdick and Jackson "Distilled
in Glass" or equivalent, stored in original containers and used as received.
6.3.2 Acetone--Pesticide quality. Burdick and Jackson "Distilled
in Glass" or equivalent, stored in original containers and used as received.
6.3.3 Water--Deionized and then glass-distilled, stored in hexane-
rinsed glass containers with TFE@-lined screw caps.
58
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6.3.4 Sodium sulfate (Na2S04)--Anhydrous, granular. Clean by
overnight Soxhlet extraction with hexane, drying in a 110°C oven, and then
heating to 650°C for 2 hr. Store in 110°C oven or in glass jar closed with
TFE®-lined screvj cap.
6.3.5 Sulfuric acid (I^SO^)--Concentrated, ACS reagent grade or
equivalent.
6.3.6 Antimony pentach-loride (SbCl5)--Baker Analyzed Reagent or
equivalent.
6.3.7 Hydrochloric acid (HC1) solution--ACS reagent grade or
equivalent, 507= in water.
6.3.8 Glass wool—Cleaned by thorough rinsing with hexane, dried
U a 110°C oven, and stored in a hexane-rinsed glass jar with TFE©-lined cap.
6.3.9 Decachlorobiphenyl--RFP Corp., No. RPC-60, or equivalent.
6.3.10 Compressed nitrogen—Prepurified.
6.3.11 Carborundum boiling stones--Hengar Co. No. 133-B or equiv-
alent, rinsed with hexane.
7. Procedure
Caution: Section 7.1.1 should be done in the laboratory.
7.1 Sampling. The sampling shall be conducted by competent personnel
experienced with this test procedure and cognizant of 'the constraints of the
analytical techniques for PCBs, particularly contamination problems.
7.1.1 Pretest preparation. All train components shall be main-
tained and calibrated aqcording to the procedure described in APTD-0576,
unless otherwise specified herein.
7.1.1.1 Cleaning glassware. All glass parts of the train
upstream of and including the adsorbent tube, should be cleaned as described
in Section 3A of the 1974 issue of "Manual of Analytical Methods for Analysis
of Pesticide Residues in Human and Environmental Samples." Special care
should be devoted to the removal of residual silicone grease sealants on
ground glass connections of used glassware. These grease residues should be
removed by soaking several hours in a chromic acid cleaning solution prior
to routine cleaning as described above.
59
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7.1.1.2 Solid adsorbent tuba. Weigh 7.5 g of Florisil, ac-
tivated within the last 30 days and still warm from storage in a 110°C oven,
into the adsorbent tube (pre-rinsed with hexane) with a glass wool plug in
the downstream end. Place a second glass wool plug in the tube to hold the
sorbent in the tube. Cap both ends of the tube with ground glass caps. These
caps should not be removed until the tube is fitted to the train immediately
prior to sampling.
7.1.2 Preliminary determinations. Select the sampling site and
the minimum number of sampling points according to Method 1 or as specified
by the Administrator. Determine the stack pressure, temperature, and the
range of velocity heads using Method 2 and moisture content using Approxi-
mation Method 4 or its alternatives for the purpose of making isokinetic
sampling rate calculations. Estimates may be used. However, final results
will be based on actual measurements made during the test.
Determine the molecular weight of the stack gases using Method 3.
Select a nozzle size based on the maximum velocity head so that
isokinetic sampling can be maintained at a rate less than 0.75 cfm. It is
not necessary to change the nozzle size in order to maintain isokinetic
sampling rates. During the run, do not change the nozzle size.
Select a suitable probe length such that all traverse points can
be sampled. Consider sampling from opposite sides for large stacks to re-
duce the length of probes.
Select a sampling time appropriate for total method sensitivity
and the PCB concentration anticipated. Sampling times, should generally fall
within a range of 2 to 4 hr.
It is recommended that a buzzer-timer be incorporated in the con-
trol box (see Figure 1) to alarm the operator to move the probe to the next
sampling point.
In some circumstances, e.g., short batch processes, it may be
necessary to sample through two or more batches to obtain sufficient sample
volume. In these cases, sampling should cease during loading/unloading of
the furnace.
7.1.3 Preparation of collection train. During preparation and
assembly of the sampling train, keep all train openings where contamination
can enter covered until just prior to assembly or until sampling is about to
begin. Immediately prior to assembly, rinse all parts of the train upstream
of the adsorbent tube with hexane.
60
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the probe with heat resistant tape or by some other method at points
indicating the proper distance into the stack or duct for each sampling
point.
Place 2'00 ml of water in each of the first two impingers, and
.£ave the third irnpinger empty. CAUTION: do not use sealant greases in
assembling the train. If the preliminary moisture determination shows that
the stack gases are saturated or supersaturated, one or two additional empty
impingers should be added to the train between the third impinger and the
Florisil tube. See Section 10.1. Place approximately 200 to 300 g or more,
if necessary, of silica gel in the last impinger. Weigh each inroinger (stem
included) and record the weights on the imningers and on the data sheet.
Unless otherwise specified by the Administrator, attach a tempera-
ture probe to the metal sheath of the sampling probe so that the sensor is
at Least 2.5 cm behind the nozzle and pitot tube and does not touch any
metal.
Assemble the train as shown in Figure A-l. Through all parts of
th:..j method use of sealant greases such as stopcock grease to seal ground
glass joints must be avoided.
Place crushed ice around the impingers.
7.1.4 Leak check procedure--After the sampling train has been as-
sembled, turn on and set (if applicable) the probe heating system(s) to reach
a temperature sufficient to avoid condensation in the probe. Allow time for
the temperature to stabilize. Leak check the train at 'the sampling site by
plugging the nozzle and pulling a 380 mm Hg (15 in. Eg) vacuum. A leakage
rate in excess of 47, of the average sampling rate of 0.0057 nP/min (0.02 cfm)
whichever is less, is unacceptable.
The following leak check instruction for the sampling train de-
scribed in APTD-0576 and APTD-0581 nay be helpful'. Start the pump with by-
pass valve fully open and coarse adjust valve completely closed. Partially
open the coarse adjust valve and slowly close the bypass valve until 380 mm
Hg (15 in. Hg) vacuum is reached. Do not reverse direction of bypass valve.
This will cause water to back up into the probe. If 380 mm Hg (15 in. Hg)
is exceeded, either leak check at this higher vacuum or end the leak check
as described below and start over.
When the leak check is completed, first slowly remove the plug
from the inlet to the probe and immediately turn off the vacuum pump. This
prevents the water in the impingers from being forced backward into the
probe.
61
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Leak checks shall be conducted as described above prior to each
test run and at the completion of each test run. If leaks are found to be
in excess of the acceptable rate, the test will be considered invalid. To
reduce lost tine due to leakage occurrences, it is recommended that leak
checks be conducted between port changes.
7.1.5 Train operation—During the sampling run, an isokinetic
sampling rate within 107., or as specified by the Administrator, of true iso-
kinetic shall be maintained. During the run, do not change the nozzle or
any other part of the train in front of and including the Florisil tube.
For each run, record the data required on the data sheets. An
example is shown in Figure A-3. Be sure to record the initial dry gas meter
reading. Record the dry gas meter readings at the beginning and end of each
sampling time increment, when changes in flow rates are made, and when sam-
pling is halted. Take other data point readings at least once at each sam-
ple point during each time increment and additional readings when significant
changes (20% variation in velocity head readings) necessitate additional ad-
justments in flow rate. Be sure to level and zero the manometer.
Clean the portholes prior to the test run to minimize chance of
sampling deposited material. To begin sampling, remove the nozzle cap,
verify (if applicable) that the probe heater is working and up to tempera-
ture, and that the pitot tube and probe are properly positioned. Position
the nozzle at the first traverse point with the tip pointing directly into
the gas stream. Immediately start the pump and adjust the flow to isokinetic
conditions. Nomographs are available for sampling trains using type S pitot
tubes with 0.85 + 0.02 coefficients (C ), and when sampling in air or a stack
gas with equivalent density (molecular weight, M^, equal to 29+4), which
aid in the rapid adjustment of the isokinetic sampling rate without excessive
computations. APTD-0576 details the procedure for using these nomographs.
If C and M^ are outside the above stated ranges, do not use the nomograph
unless appropriate steps are taken to compensate for the deviations.
When the stack is under significant negative pressure (height of
impinger stem), take care to close the coarse adjust valve before inserting
the probe into the stack to avoid water backing into the probe. If neces-
sary, the pump may be turned on with the coarse adjust valve closed.
When the probe is in position, block off the openings around the
probe and porthole to prevent unrepresentative dilution of the gas stream.
Traverse the stack cross section, as required by Method 1 or as
specified by the Administrator. To minimize chance of extracting deposited
material, be careful not to bump the probe nozzle into the stack walls when
sampling near the walls or when removing or inserting the probe through the
portholas.
62
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FIELD DATA
PLANT.
DAT£_
SAMPLING LOCATION.
SAMPLE TYPE _____
RUN NUMBER .
OPERATOR
AMBIENT TEMPERATURE
BAROMETRIC PRESSURE .
STATIC PRESSURE. (Pjl_
FILTER NUMBER Is)
PliOBE LENGTH AND TYPE.
NOZZLE I D _____ _ .
ASSUMED MOISTURE.'. _
SAMPLE OOX NUMBER _
METER BOX NUMBER __
METER 4He _
C FACTOR. _
PROBE HEATER SETTING
HEATER BOX SETTING
REFERENCE AP
SCHEMATIC OF TRAVERSE POINT LAYOUT
READ AND RECORD ALL DATA EVERY.
MINUTES
TRAVERSE
POINT
NUMBER
1
^v CLOCK TIME
>7FLINC \CLOCK,
TIME. mm N^
_
GAS METER READING
(VBI. IIJ
VELOCITY
HEAD
Upjl. in. H20
ORIFICE PRESSURE
DIFFERENTIAL
(AH), in. tl^Ol
DESIRED
.
ACTUAL
STACK
TEMPERATURE
(TSI."F
DRYGAS METER
TEMPERATURE
INLET
to
COMML H r S
fl'A iDuil ?3'j
i n
Figure A-3. Field Data Sheet
-------
During the test run, make periodic adjustments to keep the probe
temperature at the proper value. Add more ice and,'if necessary, salt to
the ice bath, to maintain a temperature of less than 20°C (68°F) at the
impinger/silica gel outlet, to avoid excessive moisture losses. Also, peri-
odically check the level and zero of the manometer.
If the pressure drop across the train becomes high enough to cake
isokinetic sampling difficult to maintain, the test run should be terminated.
Under no circumstances should the train be disassembled during a test run to
determine and correct causes of excessive pressure drops.
At the end of the sample run, turn off the pump, remove the probe
and nozzle from the stack, and record the final dry gas meter reading. Per-
form a leak check.* Calculate percent isokinetic (see calculation section)
to determine whether another test run should be made. If there is difficulty
in maintaining isokinetic rates due to source conditions, consult with the
Administrator for possible variance on the isokinetic rates.
7.1.6 Blank train—For each series of test runs, set up a blank
train in a manner identical to that described above, but with the nozzle
capped with aluminum foil and the exit end of the last impinger capped with
a ground glass cap. Allow the train to remain assembled for a period equiv-
alent to one test run. Recover the blank sample as described in Section 7.2.
7.2 Sample recovery. Proper cleanup procedure begins as soon as the
probe is removed from the stack at the end of the samp'ling period.
When the probe can be safely handled, wipe off all external par-
ticulate matter near the tip of the probe nozzle. Remove the probe from the
train and close off both ends with aluminum foil. Cap off the inlet to the
train with a ground glass cap.
Transfer the probe and impinger assembly to the cleanup area. ThLs
area should be clean and protected from the wind so that the chances of con-
taminating or losing the sample will be minimized.
Inspect the train prior to and during disassembly and note any ab-
normal conditions. Treat the samples as follows:
7.2.1 Adsorbent tube—Remove the Florisil tube from, the train and
cap it off with ground glass caps.
'•<.'ith acceptability of the test run to be based on the sane criterion as
in 7 1.4
64
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7.2.2 Sample container No. I — Remove the first three impingers.
Wipe off the outside of each impinger to remove excessive water and other
debris, weigh (stem included), and record the weight on data sheet. Pour
the contents directly into container No. 1 and seal.
7.2.3 Sample container No. 2--Rinse each of the first three im-
pingers sequentially first with 30 ml acetone and then with 30 ml hexane,
and put the rinses into container No. 2. Quantitatively recover material
deposited in the probe using 100 ml acetone and then 100 ml hexane and add
these rinses to container No. 2 and seal.
7.2.4 Silica gel container—Remove the last impinger, wipe the
outside to remove excessive water and other debris, weigh (stem included),
and record weight on data sheet. Transfer the contents to the used silica
b'el can.
7.3 Analysis. The analysis of the PCS samples should be conducted by
chemical personnel experienced in determinations of trace organics utilizing
sophisticated, instrumental techniques. All extract transfers should be
made quantitatively by rinsing the apparatus at least three times with hex-
ane and adding the rinses to the receiving container. A boiling stone should
be used in all evaporative steps to control "bumping."
7.3.1 Extraction
7.3.1.1 Adsorbent tube. Expel the entire contents of the
adsorbent tube directly onto a glass wool plug in the sample holder of a
Soxhlet extractor. Although no extraction thimble is required, a glass
thimble with a coarse-fritted bottom may be used.
Rinse the tube with 5 ml acetone and then with 15 ml hexane
and put these rinses into the extractor. Assemble the extraction apparatus
and extract the adsorbent with 170 ml hexane for at least 4 hr. The ex-
tractor should cycle 10 to 14 times per hour. After allowing the extrac-
tion apparatus to cool to ambient temperature, transfer the extract into a
Kuderna-Danish evaporator.
Evaporate the extract to about 5 ml on a steam bath and
allow the evaporator to cool to ambient temperature before disassembly.
Transfer the extract to a 50-ml separately funnel and set the funnel aside.
7.3.1.2 Sample container No. 1. Transfer the aqueous sam-
ple to a 1,000-ml separatory funnel. Rinse the container with 20 ml acetone
and then with two 20-ml portions of hexane, adding the rinses to the sep-
aratory funnel.
65
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Extract the sample with three 100 ml portions of hexane,
transferring the sequential extracts to a Kuderna-Danish evaporator.
Evaporate the extract to about 5 ml and allow the evaporator
to cool to ambient temperature before disassembly. Filter the extract through
a micro column of anhydrous sodium sulfate into the 50 ml separatory funnel
containing the corresponding Florisil extract. The micro column is prepared
by placing a small plug of glass wool in the bottom of the large portion of
a disposable pipette and then adding anhydrous sodium sulfate until the tube
is about half full.
7.3.1.3 Sample container No. 2. Transfer the organic solu-
tion into a 1,000 ml separatory funnel. Rinse the container with two 20 ml
portions of hexane and add the rinses to the separatory funnel. Wash the
sample with three 100 ml portions of water. Discard the aqueous layer and
transfer the organic layer to a Kuderna-Danish evaporator.
Evaporate the extract to about 5 ml and allow the evaporator
to cool to ambient temperature before disassembly. Filter the extract through
a micro column of anhydrous sodium sulfate into the 50 ml separatory funnel
containing the corresponding Florisil and impinger extracts.
7.3.2 Extract cleanup--Clean the combined extracts (in 50 ml
separatory funnel) by shaking with 5 ml concentrated sulfuric acid. Allow
the acid layer to separate and drain it off.
Transfer the hexane layer to a Kuderna-Danish evaporator and evap-
orate to about 5 ml. Allow the evaporator to cool to ambient temperature
before disassembly.
The extract should be essentially colorless. If it still shows
significant color, additional cleanup may be required before assaying for
PCBs. In this event, further clean the extract by liquid chromatography on
Florisil according to procedures described in Section 5A of the 1974 issue
of "Manual of Analytical Methods for Analysis of Pesticide Residues in Human
and Environmental Samples" Reduce the Florisil eluant to about 10 ml by
Kuderna-Danish evaporation techniques described above.
Transfer the cleaned extract to a 25 ml volumetric flask and di-
lute to volume with hexane. Pipette three 5.0 ml aliquots into culture
tubes for perchlorination. Retain the remaining 10 ml for later verifica-
tion, if required (see Section 10.2).
7.3.3 Extract perchlorination--Evaporate the aliquots in the cul-
ture tubes just to dryness with a gentle stream of dry nitrogen. If the ali-
quots will not evaporate to dryness, refer to Section 10.3 concerning special
cases. Add 0.2 ml antimo-ny pentachloride with a 1 ml glass-TFE® syringe and
66
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seal the tube with a TFEf®-lined screw cap. Heat the reaction mixture to 160°C
for 2 hr by placing the tube in a hole in an aluminum, block on a hot plate.
Allow the tube to cool to ambient room temperature before adding
about 2 ml of 507, HC1 in water to destroy residual antimony pentachloride.
This is a convenient "stopping point" in the perchlorination procedure.
Extract the reaction mixture by adding about 1 ml hexane to the
tube, shake, and allow layers to separate. Remove the upper hexane layer
with a disposable pipette and filter through a micro column of anhydrous
sodium sulfate directly into a 5 ml volumetric flask. Repeat the extraction
three tines for a total of four extractions. Dilute the extract to volume
with hexane.
7.3.4 PCS determination—Assay the perchlorinated extracts for
decachlorobiphenyl (DCS) by gas chromatographic comparison with DCB stan-
dard solutions and correct this result for the DCB concentration determined
for the blank train. (Column temperature and carrier gas flow parameters
of 240 = C and 30 ml/min, are typically appropriate. The concentrations of the
standard solutions should allow fairly close comparison with DCB in the sam-
ple extracts. Standards near 25 to 50 picograms/microliter may be appropriate.)
8. Calibration
Maintain a laboratory log of all calibrations.
8.1 Sampling Train
8.1.1 Probe nozzle—Using a micrometer, measure the inside dia-
neter of the nozzle to the nearest 0.025 mm (0.001 in.). Make three separate
measurements using different diameters each time and obtain the average of
the measurements. The difference between the high and low numbers shall not
exceed 0.1 mm (0.004 in.).
When nozzles become nicked, dented, or corroded, they shall be re-
shaped, sharpened, and recalibrated before use.
Each nozzle shall be permanently and uniquely identified.
8.1.2 Pitot tube—The pitot tube shall be calibrated according
to the procedure outlined in Method 2.
8.1.3 Dry gas meter and orifice meter—Both meters shall be cali-
brated according to the procedure outlined in APTD-0576. When diaphragm
67
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pumps with bypass valves are used, check for proper metering system design
by calibrating the dry gas meter at an additional flow rate of 0.0057 m3/min
(0.2 cfm) with the bypass valve fully opened and then with it fully closed.
If there is more than + 27. difference in flow rates when compared to the fully
closed position of the bypass valve, the system is not designed properly and
must be corrected.
8.1.4 Probe heater calibration--The probe heating system shall be
calibrated according to the procedure contained in APTD-0576. Probes con-
structed according to APTD-0581 need not be calibrated if the calibration
curves in APTD-0576 are used.
8.1.5 Temperature gauges—Calibrate dial and liquid filled bulb
thermometers against mercury-in-glass thermometers. Thermocouples should
be calibrated in constant temperature baths.
8.2 Analytical Apparatus
8.2.1 Gas chromatograph--Prepare a working curve from at least
five standard injections of different volumes of the DCS standard.
9. Calculations
Carry out calculations, retaining at least one extra decimal fig-
ure beyond that of the acquired data. Round off figures after final calcu-
lations .
9.1 Nomenclature
Gn = Corrected weight of DCS in nth perchlorinated aliquot (n = 1, 2, 3), pg.
Gg = Total weight of PCBs (as DCS) in sample, ug.
Cs = Concentration of PCBs in stack gas, ug/m3, corrected to standard
conditions of 20°C, 760 mm Hg (68°F, 29.92 in. Hg) on dry basis.
An ° Cross~sect:I-onal area of nozzle, m? (ft2).
Bws * Water vapor in the gas stream, proportion by volume.
I - Percent of isokinetic sampling.
^ = Molecular weight of water, 18 g/g-mole (18 Ib/lb-mole) .
Pbar " Barometric pressure at the sampling site, mm Hg (in. Hg).
68
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PS — Absolute stack gas pressure, inm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in Hg).
R = Ideal gas constant, 0.06236 nm Hg-ra3/°K-g-niole (21.83 in.
Hg-ft3/°R-lb-mole).
Tm = Absolute average dry gas meter temperature °K (*R).
Ts = Absolute average stack gas temperature °K (°R).
Tstd = Standard absolute temperature, 293°K (528°R).
V]_c = Total volume of liquid collected in impingers and silica gel, ml.
volume of water collected equals the weight increase in grams
times 1 ml/gram
V = Volume of gas sample as measured by dry gas meter, dcm. (dcf).
^m(std) ~ Volume of gas sample measured by the dry gas meter corrected to
standard conditions, dscm (dscf).
V / ,\ = Volume of water vapor in the gas sample corrected to standard
w(std) ... f f\
conditions, scrn (scr;.
Vt = Total volume of sample, ml.
V = Stack gas velocity, calculated by EPA Method 2, m/sec (ft/sec).
AH = Average pressure differential across the orifice meter, Em
(in. H20).
pw = Density of water, 1 g/ml (0.00220 Ib/ml).
9 = Total Sampling time, min.
13.6 " Specific gravity of mercury.
60 = Sec/min.
100 • Conversion to percent.
69
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9.2 Average dry gas meter temperature and average orifice pressure
drop. See data sheet (Figure A-3).
9.3 Drv gas volume. Correct the sample volume measured by the dry
gas meter to standard conditions [20°C, 760 mm Hg (68°F, 29.92 in. Hg)] by
using Equation A-l)-
V / .. = v
m(std) yra
std
•bar 13.6
Pstd
K V,
n
bar 13.6
where K = 0.3855 °K/mm Hg for metric units
= 17.65 °R/in. Hg for English units
9.4 Volume of water vaoor
VwCstd) « Vlc
K Vlc
m
Equation A-l
Equation A-2
where K = 0.00134 m /ml for metric units
= 0.0472 ft3/ml for English units
9.5 Moisture content
R - Vstd)
Vm(std) + Vw(std)
Equation A-3
If the liquid droplets are present in the gas stream assume the stream
to be saturated and use a psychrometric chart to obtain an approximation
of Che moisture percentage.
70
-------
9-6 Concentration
9.6.1 Calculate the total PCB residue (as DCB) in the sample fron
the weights of DCB in the perchlorinated aliquots according to Equation A-4-
GS . 5(G1 + G2 + G3) Equation A-4
9.6.2 Concentration of PCBs (as DCB) in stack gas. Determine the
concentration of PCBs in the stack gas according to Equation A-5.
G
cs * K Equation A-5
m(std)
where K = 35.31 ft3/m3
9.7 Isokinetic variation
9.7.1 Calculations from raw data.
100 Ts CK Vlc + (Vm/Tm) (Pfaar) + AH/13.6)]
60 9 vs Ps An
Equation A-6
where K = 0.00346 mm Hg-m3/ml-°K for metric units
= 0.00267 in. Hg-ft3/ml-°R for English units
9.7.2 Calculations from intermediate values.
x „ Ts Vm(std) Fstd
" Tstd vs 8 An Ps 60
Ts Vm(std)
K
ps vs An (1-Bws^ Equation A-7
where K = 4.323 for metric units
= 0.0944 for English units
71
-------
9.8 Acceptable results. The following range sets the Limit on accept-
able isokinetic sampling results:
If 90% < I < 110%, the results are acceptable. If the results are
low in comparison to the standards and I is beyond the acceptable range, the
Administrator may option to accept the results.
10. Special Cases
10.1 Sampling moisture saturated or supersaturated stack gases. One
or two additional modified Greenburg-Smith impingers may be added to the
train between the third impinger and the Florisil tube to accommodate addi-
tional water collection when sampling high moisture gases. Throughout the
preparation, operation, and sample recovery from the train, these additional
impingers should be treated exactly like the third impinger.
10.2 PCS verification. It is recommended that an unperchlorinated
aliquot from at least one sample be subjected to GC/MS examination to verify
that PCB isomers are present.
To accomplish this, the unperchlorinated portion of each extract
is first screened by GC with the same chromatographic system used for DCS
determination except for a cooler column temperature, typically 165 to 200°C.
The elution patterns are compared with those of commercial PCB mixtures (in
hexane solution) to determine the most similar mixture.
After determining what PCB isomers are possible present, the sam-
ple is examined by GC/MS using multiple ion selection techniques for ions
characteristic of the molecular clusters of the PCBs possibly present.
10.3 Evaporation of extracts for perchlorinatioru For cases where the
extract will not evaporate to dryness or excessive PCB loss by volatiliza-
tion is suspected, the hexane may be removed by azeotrophic evaporation from
the hexane/chloroform mixture*
Add 3 ml of chloroform to the aliquot in the culture tube. Add
a boiling chip and concentrate by slow boiling in a water bath to 1 ml.
Repeat the chloroform addition and evaporation three times in order to remove
all residual hexane. Then further concentrate (slowly) to a volume of ap-
proximately 0.1 ml. Under no circumstances should the water bath tempera-
ture be permitted to exceed 16°C or the solvent be evaporated to dryness.
The final volume (0,1 ml) may be determined with sufficient accuracy by
comparison of solvent level with another reaction vial containing 0.1 ml
of chloroform. When a volume of 0.1 ml is achieved, cap the reaction vial
L-mediately and allow to cool. Proceed with the perchlorination as described
in Section 7.3.3.
72
-------
11. References
Martin, Robert M., "Construction Details of Isokinetic Source
Sampling Equipment," Environmental Protection Agency, Air Pollution Control
Office Publication No. APTD-0581.
1973 Annual Book of ASTM Standards. Part 23, Designation: D 1179-72,
Thompson, J. F., Ed., "Analysis of Pesticide Residues in Human and
Environmental Samples," Environmental Protection Agency, Research Triangle
Park, N.C., 1974.
73
-------
Attachment F
Determination of Nitrogen Oxide Emissions
from Stationary Sources
-------
417S4
RULES AND REGULATIONS
US Sdtee Acid SUnojrt. O.OtOO V. rriM or
,uiiiUrd:ie to -O.oae N ajrurua 0.01W N NaOH wbjch
pr-nouJly been stjind~"^"
4.1 Saapflcj.
4.1.1 Preparation of rollBrUon train. Me»jur« li nl of
» percent uopropunoi Into ti» mid*«t bubbxr and 15
ol ol 3 «rant hydroren peroxide Inso each ol ti« irn
twocldii't LapiciOT. Leare the aril Budget licpinrer
in jUisimbL* ti» train u iooam In Fi:rur» >>l. Adjust
prabe c»t«r to a temperature jumc:nu to pr»Tent »^t»r
ositiensauan. Place cruaned loo and srai*r around tn«
.
4.U Leai-ebork •pr&xdart. A J«ai chicle prior to tin
•splint ran u opoonal: iow«Ter. » Irak rtwci af ur the
U3PU3K ran ii rrnnflainor- Tfc^laai-ccecJt procedure J
ti follows:
Wl:o u» prob» disconnected. plac» » fi«rtram frsAure at
tb* lni«t f th» babbler and puil i noiiim of 2s) cira
(10 In.) Ha; pi'JS or nlncti or th* outlet of tb« flow meur,
ud then ram ofl '.t» pmr.p. Tt« vacuum shall remain
lUhlt lor tt lout 30 vcondi. Carefully r»le»j» tie
ncjcn r»u*t t«Jor« rj'/«3icj the four 3Mt«r tad uj
prt7eat bart tiow of thi- unpLriirer ^Tild.
OtStr U*i-eier)c pro.-edc.-ts may b* med. tub^rt to
tbaioproral of tie AdmirutraLor. Q.3. EnrtronjrientaJ
?n>t«tioa .Anncy. Ti* xocrdi^i cued in Method 3 11
not witablo (or di*Dfrirm/-si padpa.
41."i oAmple cfU'-cr .m. Record the IrdtiAl dry rafl
rv^r rsadinj and i~i'jmetr.c proj«ui«. To i-Tin s»ra-
plirjl, pcmr.oft uh« -o o( Ua« prob* »t Lhcaimphnj poult,
«inc*ct Ci«» proiv U'» U« bubbler, and start th« pi-j^p.
Adliat ti« ?an:'jl': Ho«r to & conrtint rmu of up-
nroonASaiy 1.0 Lt'jr'nun a- '^iicat«63° F) or Vos. At to*
concioalon ot e*ch rjn, tarn ot? t!v» pump, remoTe prob«
(rem th« rt«fc ind record th« ftn»J readings. Conduct &
Wtchxku'.n Section 4.1.2. (Ttu> l«4X check Ij n»nii»-
lorjr.) Ii a nMi^: Is found, 7014 ^b* t«cx mn. Drain ib.« lc«
t»lb. tnd pursre UM ramilram put o/ tbo cnin by dr»w-
Ins cle&a inibient Mr inrou£j3 UM 7y5t&a for 15 izinuCea
ltth« 5»mpUru rnu.
Claan ambient lir can b« pnjrid»d by p&sstni air
Ummfb a chnrcoil flJur or uirough an tr_r» midg;l
topln^sr with 13 ml of 3 psrcant HjOi. The t««r nay
opt to simply DJ* idblftut air, witbo^it punflc*iloo-
4.2 SaiopU RecoTrary- D'jconnect tbo l-Tipuiion afL«t
purjinj. Ducvd theccntanuof Lb«nudget babbier. Pour
tbi con^au of tba tsJdjst tnpinxtn Into a leak-trw
wlT«thylan« bottl* for ihiprDAot. Rinaath* Lore«mjio''Jd abe4t. U a
amount of k-xjumo t-Lj occurred, dtier TO id UM sampk*
or me m>tbod>, snbWci to UM appnrral of Lba Admini>-
truer, U) correct tic imJ ncolu.
Traailw Ui« nmtenu o< tiw stora«« container to a
ICXVnl Tolnmetnc fliik and ciltnci to *i»«Jy 100 nl
vlth dskiaiiod, diitliUd irua. Plpetis a a>mJ aliquot of
tijj somaoQ into a ISO-mi Etimmeyar flaik, add SO ml
ol 100 percent bo propane 1 and nro to [our drops ot tbonn
h&caur, and titrau to o pink endpaint linrn! 0 0100 N
banam percWorat*. R*p«ai aad arerufe tb« titration
7oluzi*i. Run »b'juiiwTJj each seri«ol samples. JUptt-
cal4 tltrations tsun &$ra« irlthin 1 p-arcent OT 0^ mi,
»hjcio?«r li itrf ar.
(Non.— Prot*« tho 0.0100 N Imrinjn perchlorau
soJuCon from eraponaon at ail time*.) •
i.
j: pl»c« a racoon j»u«« at Us« IrJet to tie drylrn
mb« and pull a Tacaora ol liO ™m tio in.) Hi: piuc or
pmcn otf tn« outlet ar th« flow m«trr. and tb«n tnrn off
th« parop. Tha racnua ihail ranjun ^abl*: for at >**n
30 xcoodju CareluUy nle&H tho rac&unz gau(t beioro
rt\rt.fmt Lto Dow m at leu: fly* rerotc-
Lioiu o/ tie dry ja» mtier per ran. CaicnLit* tie alion-
aoQ (actor, X vwet ten mettr v»--3a.-ometrK prensure at tb« e3lt orlflci o( ti*
dry fM meur. mm Hj (In. H().
ab«luu> prewrm, 760 mm H»
eLtr abaohit* Umperatara,
,_ _
abaoint* Umperarore, 3r K
(S3* H).
V.-Volom« of sampte ali m^k5um
rmng tie pbftooldi2uUoaio*cid (PD3) prooBdare.
U AppUcuburcy. Till metnod U applicable to tins
meuuraiaant of oicrornn, oj^ded ejnittMi Crom
source*. Tie range oX to« metiod bJU boen
to Ni 2 to 4OO mfllirrajns N 0 , (ai NOO per dry s
cubic m*ter, wrUxxrc barin( to dilate La» mmpto.
2.1 SAID pilot (a» Tlcun 7-1). Other grab
rjntemj or equipment, capaMa of EDcejumna ounpie
yolome to wltnin -^-in p«rc«Gt acd ^*n^^rjnn a someiACtt
sample Totom* to aUow anAlrtl£&l n prod del b»ltT7 to
wltbla ±j permt, wOl bo conjiderol accepxabke tit/at-
niUre* iub|«rt to appro-rai ot ti« Administrator. O -3,
EoruTjomenial PnrucdOQ Armey. T6»
«qulpmeot U oaed In nunpllngt
2-LJ Probe. Barceflie&U Slav tnWtui,
heated to parent -water coodinaiaoQ acxl
with an ln-ctack or ocd-ctack filter to mmoTe p
matter (a plo« ot fl*J« -wooi i3 swiatoolary loe tiia
tmrpote). Suinleoa ttoel or TefVm ' tnMnv muy aim bo
used for UM pro&a. Haafiiat Ll not naoeaaanr U IJM pro
remain] dry damn UM {XirpUn period,
i Mention ot trad* Maw* or jporifla predncta 6ea at*
eotutturte ejxloneioent by UM SnTtrcsuacotkt P»»
to: don A^caey.
FEDE»AL »EOISn», VOU 42, NO. 160—THURSDAY, AUGUST II, 1977
-------
RULES AND REGULATIONS
417S5
SQUEEZE BULB
PROSE
. FLASK VALV
FILTER
GROUND-GLASS SOCXfT,
NO. 12/5
110
>WAY STCPCOCK--
T-flOfS. I prssx,
2-mm BORE, 8-nvn QO
FLASX
PURGE
THERMOMETER
CCN£,
GRCUrVO-GL&SS
STANDATO TAPEH,
SL££VH Ma 2
210 mm
GROUND-GLASS
SOCKET. § NO. 12/5
PYR£X
— -fO&M ENCASEMENT
BOILING RASX -
2-UTOCROUND-907TOM. SHCOT NECX,
WITH J SLEWS NO. 24/40
Figure 7-1. Sampling train, flask valve, and flask.
Z.tS Collection JiasX Two-liter boraule&te, round
bot:om fM'I, with short seek and 24/40 standard t&ptr
opening, protected asaffiss impkrwon or bresta^-a,
2.L3 Flsji Valra. T-bor» stopcock connected to &
2ViO sundard tipw Joint.
2.1.4 TempersCOT Gacg«. Dial-type thermoowter. or
other Umperacurs glut*, capablo of measuring I* C
(2* F) Intervals from -i to SO* C (24 to 125- F).
2.1.J Vacuum Line, Tcbina capable ol wlibstandlOf
»vacumo(7JmmHi[ (3m. HS) absoloM pressure, wllh
T" connection and T-bora rtopewk.
2.1.8 Vacuum G»tw». G-tube mocotooter. 1 metw
(36 la.), vtth 1-na (0.1-iaJ diTtsiocs. or other esairo
eapah'.e o( aieasurinz pressure to wiOiin i2J ma Hz
(0.10 in. Hj).
2.1.7 Pump. C»p«ta» ol eTBCTifttlBS tSs coU«ctioa
flssi to » pre«a.-» sqaal to or laa than 75 me* HLg U in.
H?) ntuoluM. • •
2.1.8 SqueeieBulb. Oc»-w»y.
2.1.9 Voluo«trt: Pipette. 23 ml.
2.1.10 ECop:ock »ml Gro-ccd Joint Qreaaa, A high-
Tuuuja, hiph-i«=ip«ftrar» chlorofluorocftrbon gros* Li
requlrwl. Halocarbon 05-53 iiu tw«n (ound to b« eflsty TO.
2.1.11 B&rom«lar. M«rtnr?, uieroid, or other b&rom-
et«r c»pabls ol naasurva^ »tmosph«nc pressure to Tithun
2J C51 Kg (0.1 10. Hi). In CADT csMa. tne b&fomacrb
f»4l;a4ic»7b«obt£jned(rom & ctaroy nAliontl Tefitbcr
Mrrict nation, la which cfc» tb* station valu« (whicn Is
th« ib*jiun bammetrie pressure) shall be re quisled uid
•n »dJU3ttnent lor' elzTaiiou dlSsrenws b»lw«n tb«
»»t6er iduon ajd sa=pUng point shali be appLeJ it a
«»t« o( minus 2J mm Eg (0.1 la. Hg) per 30 m (1W ft)
devjuou incms«, or vice rena (or elevation der.Tas*.
t2 Jimpl» RaxTerr. Th« loUowlng tqulpment Is
rtqulrM for stepl* reeovery:
•>•} 1 Cndtis'.ed CyUndtr. SO ml ^tii 1-m! dl-»tslon».
2i2 Etarije Containers. L«»k-tr» polyethylen«
iij wMh Bottle. Polyethylene or glass. •
2.2.1 Glass Stlrrinl Rod.
2.2J Twt Psper (or Indicating pH. To COTST th« pH
nag* o(7 to 14. ,
7^ Analysis. Tor lh« analrus. the followinj Kjait>- .
Dtab«, ITi- to 2SO-mi
capacity vlth Up for pounny. oo« lor each jamcle and
each standard. Th« COOTS No. liOO» (shaiiow-form. )W
ml) has be«o found to b« satisiactorf. Altfraativet^.
polynietbyl p«nten« beakers (Naije No. 12O3, 150 ml), or
glass beaiirs (liO ml) may b« ussd. Wtwi glou b«t?r3
are Lu«d. etchind of the beakers may cause »Ud m&Uer
to b« pnomt In the analytical nao, the iolidj sbouJd t»
removed by filtration (s*» 3*ctlon 4J).
2-1. .1 Seram Bath. Low-tempenUonsov-mor thermiv
staUcalJy controUM hot plate kept betow 70° C UW 7)
arc accepublo alternatives.
2-H Dropping Pipette or Dropper. Thrw reqmrsd.
SJJ.4 Polyethylen* Policeman. One for each lampi®
and each standard.
2J.S GraduatBd Cylinder. 100ml with 1-tol dl-rtiionj.
2.a.7 Volumetric Flastj. M ml (one for me ft saaplf),
100 ml (one for each sample and ear h ^taAdard. and ooa
for tho vorklox studied O'Oi souiuoa), and 1000 ml
(one).
2JJ Spectrophotomite. To measore sbaorb&nca at
410 run.
2.3.9 Oraduatcd PIp-rte. 10ml with 0.1-tnl dlTtsloos.
2.S.10 Te |