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Federal Register / Vol. 65, No.

201 / Tuesday, October 17, 2000 / Rules and Regulations 61993

the original endpoint was in error. It is test differs by more than 5 percent, void 0.010, add a few ml of 0.1 N iodine
recommended that persons conducting this the sample; if not, proceed to perform solution if it is low, or a few ml of water
test perform several titrations to be able to the calculations. if it is high, and standardize again.
correctly identify the endpoint. The 16.12 Calibrations and Repeat the titration until replicate
importance of this should be recognized Standardizations.
because the results of this analytical
values agree within 0.05 ml. Take the
16.12.1 Rotameter and Barometer. average volume to calculate the
procedure are extremely sensitive to errors in
titration. Same as Method 11, Sections 10.1.3 and normality to three decimal figures using
10.1.4. Equation 16A–6.
16.10 Sample Analysis. Sample 16.12.2 Na2S2O3 Solution, 0.1 N. 16.12.4 Critical Orifice. Calibrate the
treatment is similar to the blank Standardize the 0.1 N Na2S2O3 solution critical orifice using the sampling train
treatment. Before detaching the stems as follows: To 80 ml water, stirring shown in Figure 16A–4 but without the
from the bottoms of the impingers, add constantly, add 1 ml concentrated H2S cylinder and vent rotameter.
20.0 ml of 0.01 N iodine solution H2SO4, 10.0 ml of 0.100 N KH(IO3)2 and Connect the soap bubble meter to the
through the stems of the impingers 1 g potassium iodide. Titrate Teflon line that is connected to the first
holding the zinc acetate solution, immediately with 0.1 N Na2S2O3 until impinger. Turn on the pump, and adjust
dividing it between the two (add about the solution is light yellow. Add 3 ml the needle valve until the vacuum is
15 ml to the first impinger and the rest starch solution, and titrate until the blue higher than the critical vacuum
to the second). Add 2 ml HCl solution color just disappears. Repeat the determined in Section 16.7.4. Record
through the stems, dividing it as with titration until replicate analyses agree the time required for gas flow to equal
the iodine. Disconnect the sampling within 0.05 ml. Take the average the soap bubble meter volume (use the
line, and store the impingers for 30 volume of Na2S2O3 consumed to 100-ml soap bubble meter for gas flow
minutes. At the end of 30 minutes, rinse calculate the normality to three decimal rates below 100 ml/min, otherwise use
the impinger stems into the impinger figures using Equation 16A–5. the 500-ml soap bubble meter). Make
bottoms. Titrate the impinger contents 16.12.3 Iodine Solution, 0.01 N.
three runs, and record the data listed in
with 0.01 N Na2S2O3. Do not transfer the Standardize the 0.01 N iodine solution
Table 16A–1. Use these data to calculate
contents of the impinger to a flask as follows: Pipet 20.0 ml of 0.01 N
the volumetric flow rate of the orifice.
because this may result in a loss of iodine solution into a 125-ml
iodine and cause a positive bias. 16.13 Calculations.
Erlenmeyer flask. Titrate with standard
16.11 Post-test Orifice Calibration. 0.01 N Na2S2O3 solution until the 16.13.1 Nomenclature.
Conduct a post-test critical orifice solution is light yellow. Add 3 ml starch Bwa = Fraction of water vapor in ambient
calibration run using the calibration solution, and continue titrating until the air during orifice calibration.
procedures outlined in Section 16.12.4. blue color just disappears. If the CH2S = H2S concentration in cylinder
If the Qstd obtained before and after the normality of the iodine tested is not gas, ppmv.

mg 24.05L 1 mole 1g 10 3 mL 10 3 µL
K 2 = 32.03
meq mole 64.06g 10 3 mg L l mL
12025 µL
=
meq
Ma = Molecular weight of ambient air saturated at impinger temperature, g/g-mole.
Ms = Molecular weight of sample gas (nitrogen) saturated at impinger temperature, g/g-mole.
Note: (For tests carried out in a laboratory where the impinger temperature is 25 °C, Ma = 28.5 g/g-mole and
Ms = 27.7 g/g-mole.)
NI = Normality of standard iodine solution (0.01 N), g-eq/liter.
NT = Normality of standard Na2S2O3 solution (0.01 N), g-eq/liter.
Pbar = Barometric pressure, mm Hg.
Pstd = Standard absolute pressure, 760 mm Hg.
Qstd = Average volumetric flow rate through critical orifice, liters/min.
Tamb = Absolute ambient temperature, °K.
Tstd = Standard absolute temperature, 293 °K.
θs = Sampling time, min.
θsb = Time for soap bubble meter flow rate measurement, min.
Vm(std) = Sample gas volume measured by the critical orifice, corrected to standard conditions, liters.
Vsb = Volume of gas as measured by the soap bubble meter, ml.
Vsb(std) = Volume of gas as measured by the soap bubble meter, corrected to standard conditions, liters.
VI = Volume of standard iodine solution (0.01 N) used, ml.
VT = Volume of standard Na2S2O3 solution (0.01 N) used, ml.
VTB = Volume of standard Na2S2O3 solution (0.01 N) used for the blank, ml.
16.13.2 Normality of Standard Na2S2O3 Solution (0.1 N).

1
NT = Eq. 16A-5
mL Na 2 S2 O 3 consumed

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61994 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

16.13.3 Normality of Standard Iodine Solution (0.01 N).

N T VT
NI = Eq. 16A-6
VI
16.13.4 Sample Gas Volume.

Vm (std ) = Qstd Θ s (1 − Bwa )
Ma
Eq. 16A-7
Mb

16.13.5 Concentration of H2S in the 4. Blosser, R.O., H.S. Oglesby, and A.K. Assurance Division, U.S. Environmental
Gas Cylinder. Jain. A Study of Alternate SO2 Scrubber Protection Agency, Research Triangle Park,
Designs Used for TRS Monitoring. A Special NC 27711.
17.0 References Report by the National Council of the Paper 8. National Council of the Paper Industry
Industry for Air and Stream Improvement, for Air and Stream Improvement. An
K N T (VTB − VT ) Inc., New York, NY. July 1977. Investigation of H2S and SO2. Calibration
C H 2S = Eq. 16A-8
Vm (std ) 5. Curtis, F., and G.D. McAlister. Cylinder Gas Stability and Their
Development and Evaluation of an Standardization Using Wet Chemical
Oxidation/Method 6 TRS Emission Sampling Techniques. Special Report 76–06. New
1. American Public Health Association,
Procedure. Emission Measurement Branch, York, NY. August 1976.
American Water Works Association, and
Emission Standards and Engineering
Water Pollution Control Federation. Standard 9. National Council of the Paper Industry
Methods for the Examination of Water and Division, U.S. Environmental Protection
for Air and Stream Improvement. Wet
Wastewater. Washington, DC. American Agency, Research Triangle Park, NC 27711.
Chemical Method for Determining the H2S
Public Health Association. 1975. pp. 316– February 1980.
Concentration of Calibration Cylinder Gases.
317. 6. Gellman, I. A Laboratory and Field
Technical Bulletin Number 450. New York,
2. American Society for Testing and Study of Reduced Sulfur Sampling and
Monitoring Systems. National Council of the NY. January 1985. 23 pp.
Materials. Annual Book of ASTM Standards.
Paper Industry for Air and Stream 10. National Council of the Paper Industry
Part 31: Water, Atmospheric Analysis.
Improvement, Inc., New York, NY. for Air and Stream Improvement. Modified
Philadelphia, PA. 1974. pp. 40–42.
3. Blosser, R.O. A Study of TRS Atmospheric Quality Improvement Technical Wet Chemical Method for Determining the
Measurement Methods. National Council of Bulletin No. 81. October 1975. H2S Concentration of Calibration Cylinder
the Paper Industry for Air and Stream 7. Margeson, J.H., J.E. Knoll, and M.R. Gases. Draft Report. New York, NY. March
Improvement, Inc., New York, NY. Technical Midgett. A Manual Method for TRS 1987. 29 pp.
Bulletin No. 434. May 1984. 14 pp. Determination. Source Branch, Quality BILLING CODE 6560–50–P

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Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations 61995

18.0 Tables, Diagrams, Flowcharts, and Validation Data

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61996 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

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Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations 61997

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61998 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

BILLING CODE 6560–50–C

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Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations 61999

Date llllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
Critical orifice ID lllllllllllllllllllllllllllllllllllllllllllllllllllllllll
Soap bubble meter volume, Vsbll liters
Time, θsb
Run no. 1 ll min ll sec
Run no. 2 ll min ll sec
Run no. 3 ll min ll sec
Average ll min ll sec
Covert the seconds to fraction of minute:
Time = ll min + ll Sec/60 = ll min
Barometric pressure, Pbar = ll mm Hg
Ambient temperature, t amb = 273 + ll °C = ll °K = ll mm Hg. (This should be approximately 0.4 times barometric pressure.)
Pump vacuum,

Vsb (std ) =
Vsb Tstd Pbar 10 −3( )
Tamb Pstd
= - - - - - - - - - - liters
Vsb (std )
Q std =
Θ sb
= - - - - - - - - - - liters/ min

Table 16A–1. Critical Orifice Calibration Data
Method 16B—Determination of Total Reduced Sulfur Emissions From Stationary Sources
This method does not include all of the specifications (e.g., equipment and supplies) and procedures (e.g.,
NOTE:
sampling and analytical) essential to its performance. Some material is incorporated by reference from other methods
in this part. Therefore, to obtain reliable results, persons using this method should have a knowledge of at least the
following additional test methods: Method 6C, Method 16, and Method 16A.
1.0 Scope and Application
1.1 Analytes.

Analyte CAS No.

Total reduced sulfur (TRS) including: N/A
Dimethyl disulfide (DMDS), [(CH3)2S2] ......................................................................................................................................... 62–49–20
Dimethyl sulfide (DMS), [(CH3)2S] ................................................................................................................................................ 75–18–3
Hydrogen sulfide (H2S) ................................................................................................................................................................. 7783–06–4
Methyl mercaptan (MeSH), [CH4S] .............................................................................................................................................. 74–93–1
Reported as: Sulfur dioxide (SO2) ....................................................................................................................................................... 7449–09–5

1.2 Applicability. This method is chromatography (GC) using flame 4.3 Carbon monoxide (CO) and
applicable for determining TRS photometric detection (FPD). carbon dioxide (CO2) have substantial
emissions from recovery furnaces desensitizing effects on the FPD even
3.0 Definitions. [Reserved] after dilution. Acceptable systems must
(boilers), lime kilns, and smelt
dissolving tanks at kraft pulp mills, and 4.0 Interferences demonstrate that they have eliminated
from other sources when specified in an this interference by some procedure
applicable subpart of the regulations. 4.1 Reduced sulfur compounds such as eluting these compounds before
The flue gas must contain at least 1 other than those regulated by the the SO2. Compliance with this
emission standards, if present, may be requirement can be demonstrated by
percent oxygen for complete oxidation
measured by this method. Therefore, submitting chromatograms of calibration
of all TRS to SO2.
carbonyl sulfide, which is partially gases with and without CO2 in diluent
1.3 Data Quality Objectives. oxidized to SO2 and may be present in gas. The CO2 level should be
Adherence to the requirements of this a lime kiln exit stack, would be a approximately 10 percent for the case
method will enhance the quality of the positive interferant. with CO2 present. The two
data obtained from air pollutant chromatograms should show agreement
4.2 Particulate matter from the lime
sampling methods. within the precision limits of Section
kiln stack gas (primarily calcium
2.0 Summary of Method carbonate) can cause a negative bias if 13.0.
it is allowed to enter the citrate 5.0 Safety
2.1 An integrated gas sample is scrubber; the particulate matter will
extracted from the stack. The SO2 is cause the pH to rise and H2S to be 5.1 Disclaimer. This method may
removed selectively from the sample absorbed before oxidation. Proper use of involve hazardous materials, operations,
using a citrate buffer solution. The TRS the particulate filter, described in and equipment. This test method may
compounds are then thermally oxidized Section 6.1.3 of Method 16A, will not address all of the safety problems
to SO2 and analyzed as SO2 by gas eliminate this interference. associated with its use. It is the

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62000 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

responsibility of the user of this test 7.0 Reagents and Standards compounds and less than 10 ppmv total
method to establish appropriate safety Same as in Method 16, Section 7.0, hydrocarbons. The gas may be generated
and health practices and determine the except for the following: from a clean-air system that purifies
applicability of regulatory limitations 7.1 Calibration Gas. SO2 permeation ambient air and consists of the
prior to performing this test method. tube gravimetrically calibrated and following components: diaphragm
5.2 Hydrogen Sulfide (H2S). A certified at some convenient operating pump, silica gel drying tube, activated
flammable, poisonous gas with the odor temperature. These tubes consist of charcoal tube, and flow rate measuring
of rotten eggs. H2S is extremely hermetically sealed FEP Teflon tubing device. Gas from a compressed air
hazardous and can cause collapse, in which a liquefied gaseous substance cylinder is also acceptable.
coma, and death within a few seconds is enclosed. The enclosed gas permeates 8.0 Sample Collection, Preservation,
of one or two inhalations at sufficient through the tubing wall at a constant Storage, and Transport
concentrations. Low concentrations rate. When the temperature is constant,
irritate the mucous membranes and may calibration gases covering a wide range 8.1 Pretest Procedures. Same as in
cause nausea, dizziness, and headache of known concentrations can be Method 15, Section 8.1.
after exposure. generated by varying and accurately 8.2 Sample Collection. Before any
measuring the flow rate of diluent gas source sampling is performed, conduct
6.0 Equipment and Supplies passing over the tubes. In place of SO2 a system performance check as detailed
6.1 Sample Collection. The sampling permeation tubes, cylinder gases in Section 8.4.1 to validate the sampling
train is shown in Figure 16B–1. containing SO2 in nitrogen may be used train components and procedures.
Modifications to the apparatus are for calibration. The cylinder gas Although this test is optional, it would
accepted provided the system concentration must be verified significantly reduce the possibility of
performance check in Section 8.4.1 is according to Section 8.2.1 of Method 6C. rejecting tests as a result of failing the
met. The calibration gas is used to calibrate post-test performance check. At the
the GC/FPD system and the dilution completion of the pretest system
6.1.1 Probe, Probe Brush, Particulate system. performance check, insert the sampling
Filter, SO2 Scrubber, Combustion Tube, 7.2 Recovery Check Gas. probe into the test port making certain
and Furnace. Same as in Method 16A, 7.2.1 Hydrogen sulfide [100 parts that no dilution air enters the stack
Sections 6.1.1 to 6.1.6. per million by volume (ppmv) or less] though the port. Condition the entire
6.1.2 Sampling Pump. Leakless in nitrogen, stored in aluminum system with sample for a minimum of
Teflon-coated diaphragm type or cylinders. Verify the concentration by 15 minutes before beginning analysis. If
equivalent. Method 11, the procedure discussed in the sample is diluted, determine the
6.2 Analysis. Section 16.0 of Method 16A, or gas dilution factor as in Section 10.4 of
chromatography where the instrument Method 15.
6.2.1 Dilution System (optional), Gas
is calibrated with an H2S permeation 8.3 Analysis. Inject aliquots of the
Chromatograph, Oven, Temperature
tube as described below. For the wet- sample into the GC/FPD analyzer for
Gauges, Flow System, Flame
chemical methods, the standard analysis. Determine the concentration of
Photometric Detector, Electrometer,
deviation should not exceed 5 percent SO2 directly from the calibration curves
Power Supply, Recorder, Calibration
on at least three 20-minute runs. or from the equation for the least-
System, Tube Chamber, Flow System, 7.2.2 Hydrogen sulfide recovery gas
and Constant Temperature Bath. Same squares line.
generated from a permeation device 8.4. Post-Test Procedures
as in Method 16, Sections 6.2.1, 6.2.2, gravimetrically calibrated and certified
and 6.3. 8.4.1 System Performance Check.
at some convenient operation Same as in Method 16A, Section 8.5. A
6.2.2 Gas Chromatograph Columns. temperature may be used. The sufficient number of sample injections
Same as in Method 16, Section 6.2.3. permeation rate of the device must be should be made so that the precision
Other columns with demonstrated such that at a dilution gas flow rate of requirements of Section 13.2 are
ability to resolve SO2 and be free from 3 liters/min (64 ft3/hr), an H2S satisfied.
known interferences are acceptable concentration in the range of the stack 8.4.2 Determination of Calibration
alternatives. Single column systems gas or within 20 percent of the emission Drift. Same as in Method 15, Section
such as a 7-ft Carbsorb B HT 100 standard can be generated. 8.3.2.
column have been found satisfactory in 7.3 Combustion Gas. Gas containing
resolving SO2 from CO2. less than 50 ppbv reduced sulfur 9.0 Quality Control

Section Quality control measure Effect

8.2, 8.3 ................ System performance check ....................................... Ensure validity of sampling train components and analytical proce-
dure.
8.1 ....................... Sampling equipment leak-check and calibration ....... Ensure accurate measurement of stack gas flow rate, sample vol-
ume.
10.0 ..................... Analytical calibration .................................................. Ensure precision of analytical results within 5 percent.

10.0 Calibration
Same as in Method 16, Section 10, except SO2 is used instead of H2S.
11.0 Analytical Procedure
11.1 Sample collection and analysis are concurrent for this method (see section 8.3).
12.0 Data Analysis and Calculations
12.1 Nomenclature.
CSO2 = Sulfur dioxide concentration, ppmv.
CTRS = Total reduced sulfur concentration as determined by Equation 16B–1, ppmv.

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Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations 62001

d = Dilution factor, dimensionless.
N = Number of samples.
12.2 SO2 Concentration. Determine the concentration of SO2, CSO2, directly from the calibration curves. Alternatively,
the concentration may be calculated using the equation for the least-squares line.
12.3 TRS Concentration.

C TRS = C SO2 d Eq. 16B-1 13.2 GC/FPD Calibration and difference of less than 4.0 percent. This
Precision. A series of three consecutive difference was not determined to be
12.4 Average TRS Concentration injections of the sample calibration gas, significant.
at any dilution, must produce results
14.0 Pollution Prevention. [Reserved]
n which do not vary by more than 5
∑ C TRS percent from the mean of the three
injections.
15.0 Waste Management. [Reserved]
i =1
Avg. C TRS = Eq. 16B-2 13.3 Calibration Drift. The
16.0 References
N 1. Same as in Method 16, Section 16.0.
calibration drift determined from the
13.0 Method Performance. mean of the three injections made at the 2. National Council of the Paper Industry
beginning and end of any run or series for Air and Stream Improvement, Inc, A
13.1 Range and Sensitivity. Coupled Study of TRS Measurement Methods.
with a GC using a 1-ml sample size, the of runs within a 24-hour period must
Technical Bulletin No. 434. New York, NY.
maximum limit of the FPD for SO2 is not exceed 5 percent.
May 1984. 12p.
approximately 10 ppmv. This limit is 13.4 System Calibration Accuracy. 3. Margeson, J.H., J.E. Knoll, and M.R.
extended by diluting the sample gas Losses through the sample transport Midgett. A Manual Method for TRS
before analysis or by reducing the system must be measured and a Determination. Draft available from the
sample aliquot size. For sources with correction factor developed to adjust the authors. Source Branch, Quality Assurance
emission levels between 10 and 100 calibration accuracy to 100 percent. Division, U.S. Environmental Protection
ppm, the measuring range can be best 13.5 Field tests between this method Agency, Research Triangle Park, NC 27711.
extended by reducing the sample size. and Method 16A showed an average BILLING CODE 6560–50–P

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62002 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

17.0 Tables, Diagrams, Flowcharts, and Validation Data

BILLING CODE 6560–50–C

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Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations 62003

Method 17—Determination of 2.0 Summary of Method flow rates than that described in APTD-
Particulate Matter Emissions From 2.1 Particulate matter is withdrawn 0581, thus necessitating the use of larger
Stationary Sources isokinetically from the source and sized nozzles, the free-space shall be 1.9
collected on a glass fiber filter cm (3⁄4-in.) with the largest sized nozzle
Note: This method does not include all of
the specifications (e.g., equipment and maintained at stack temperature. The in place.
supplies) and procedures (e.g., sampling and PM mass is determined gravimetrically 6.1.4.2 Source-sampling assemblies
analytical) essential to its performance. Some after the removal of uncombined water. that do not meet the minimum spacing
material is incorporated by reference from requirements of Figure 17–1 (or the
other methods in this part. Therefore, to 3.0 Definitions equivalent of these requirements, e.g.,
obtain reliable results, persons using this Same as Method 5, Section 3.0. Figure 2–4 of Method 2) may be used;
method should have a thorough knowledge however, the pitot tube coefficients of
of at least the following additional test 4.0 Interferences. [Reserved] such assemblies shall be determined by
methods: Method 1, Method 2, Method 3,
Method 5. 5.0 Safety calibration, using methods subject to the
approval of the Administrator.
5.1 Disclaimer. This method may 6.1.5 Condenser. It is recommended
1.0 Scope and Application involve hazardous materials, operations, that the impinger system or alternatives
1.1 Analyte. Particulate matter (PM). and equipment. This test method may described in Method 5 be used to
No CAS number assigned. not address all of the safety problems determine the moisture content of the
Note: Particulate matter is not an absolute associated with its use. It is the stack gas. Flexible tubing may be used
quantity. It is a function of temperature and responsibility of the user of this test
pressure. Therefore, to prevent variability in between the probe extension and
method to establish appropriate safety condenser. Long tubing lengths may
PM emission regulations and/or associated
and health practices and determine the affect the moisture determination.
test methods, the temperature and pressure at
which PM is to be measured must be applicability of regulatory limitations 6.2 Sample Recovery. Probe-liner
carefully defined. Of the two variables (i.e., prior to performing this test method. and probe-nozzle brushes, wash bottles,
temperature and pressure), temperature has 6.0 Equipment and Supplies glass sample storage containers, petri
the greater effect upon the amount of PM in dishes, graduated cylinder and/or
an effluent gas stream; in most stationary 6.1 Sampling Train. A schematic of
source categories, the effect of pressure
balance, plastic storage containers,
the sampling train used in this method
appears to be negligible. In Method 5, 120 °C funnel and rubber policeman, funnel.
is shown in Figure 17–1. The sampling
(248 °F) is established as a nominal reference Same as in Method 5, Sections 6.2.1
train components and operation and
temperature. Thus, where Method 5 is through 6.2.8, respectively.
specified in an applicable subpart of the
maintenance are very similar to Method 6.3 Sample Analysis. Glass weighing
standard, PM is defined with respect to 5, which should be consulted for dishes, desiccator, analytical balance,
temperature. In order to maintain a collection details. balance, beakers, hygrometer,
temperature of 120 °C (248 °F), Method 5 6.1.1 Probe Nozzle, Differential temperature sensor. Same as in Method
employs a heated glass sample probe and a Pressure Gauge, Metering System, 5, Sections 6.3.1 through 6.3.7,
heated filter holder. This equipment is Barometer, Gas Density Determination
somewhat cumbersome and requires care in respectively.
Equipment. Same as in Method 5,
its operation. Therefore, where PM 7.0 Reagents and Standards
Sections 6.1.1, 6.1.4, 6.1.8, 6.1.9, and
concentrations (over the normal range of
temperature associated with a specified 6.1.10, respectively. 7.1 Sampling. Filters, silica gel,
source category) are known to be 6.1.2 Filter Holder. The in-stack water, crushed ice, stopcock grease.
independent of temperature, it is desirable to filter holder shall be constructed of Same as in Method 5, Sections 7.1.1,
eliminate the glass probe and the heating borosilicate or quartz glass, or stainless 7.1.2, 7.1.3, 7.1.4, and 7.1.5,
systems, and to sample at stack temperature. steel. If a gasket is used, it shall be made respectively. Thimble glass fiber filters
1.2 Applicability. This method is of silicone rubber, Teflon, or stainless may also be used.
applicable for the determination of PM steel. Other holder and gasket materials 7.2 Sample Recovery. Acetone
emissions, where PM concentrations are may be used, subject to the approval of (reagent grade). Same as in Method 5,
known to be independent of the Administrator. The filter holder Section 7.2.
temperature over the normal range of shall be designed to provide a positive 7.3 Sample Analysis. Acetone and
temperatures characteristic of emissions seal against leakage from the outside or Desiccant. Same as in Method 5,
from a specified source category. It is around the filter. Sections 7.3.1 and 7.3.2, respectively.
intended to be used only when specified 6.1.3 Probe Extension. Any suitable
by an applicable subpart of the rigid probe extension may be used after 8.0 Sample Collection, Preservation,
standards, and only within the the filter holder. Storage, and Transport
applicable temperature limits (if 6.1.4 Pitot Tube. Same as in Method 8.1 Sampling.
specified), or when otherwise approved 5, Section 6.1.3. 8.1.1 Pretest Preparation. Same as in
by the Administrator. This method is 6.1.4.1 It is recommended (1) that Method 5, Section 8.1.1.
not applicable to stacks that contain the pitot tube have a known baseline 8.1.2 Preliminary Determinations.
liquid droplets or are saturated with coefficient, determined as outlined in Same as in Method 5, Section 8.1.2,
water vapor. In addition, this method Section 10 of Method 2; and (2) that this except as follows: Make a projected-area
shall not be used as written if the known coefficient be preserved by model of the probe extension-filter
projected cross-sectional area of the placing the pitot tube in an interference- holder assembly, with the pitot tube
probe extension-filter holder assembly free arrangement with respect to the face openings positioned along the
covers more than 5 percent of the stack sampling nozzle, filter holder, and centerline of the stack, as shown in
cross-sectional area (see Section 8.1.2). temperature sensor (see Figure 17–1). Figure 17–2. Calculate the estimated
1.3 Data Quality Objectives. Note that the 1.9 cm (3⁄4-in.) free-space cross-section blockage, as shown in
Adherence to the requirements of this between the nozzle and pitot tube Figure 17–2. If the blockage exceeds 5
method will enhance the quality of the shown in Figure 17–1, is based on a 1.3 percent of the duct cross sectional area,
data obtained from air pollutant cm (1⁄2-in.) ID nozzle. If the sampling the tester has the following options
sampling methods. train is designed for sampling at higher exist: (1) a suitable out-of-stack filtration

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method may be used instead of in-stack Use a data sheet such as the one shown wind so that the chances of
filtration; or (2) a special in-stack in Figure 5–3 of Method 5, except that contaminating or losing the sample will
arrangement, in which the sampling and the filter holder temperature is not be minimized.
velocity measurement sites are separate, recorded. 8.2.5 Save a portion of the acetone
may be used; for details concerning this 8.1.6 Calculation of Percent used for cleanup as a blank. Take 200
approach, consult with the Isokinetic. Same as in Method 5, Section ml of this acetone from the wash bottle
Administrator (see also Reference 1 in 12.11. being used and place it in a glass sample
Section 17.0). Select a probe extension 8.2 Sample Recovery. container labeled ‘‘acetone blank.’’
length such that all traverse points can 8.2.1 Proper cleanup procedure Inspect the train prior to and during
be sampled. For large stacks, consider begins as soon as the probe extension disassembly and not any abnormal
sampling from opposite sides of the assembly is removed from the stack at conditions. Treat the sample as
stack to reduce the length of probes. the end of the sampling period. Allow discussed in Method 5, Section 8.2.
8.1.3 Preparation of Sampling Train. the assembly to cool.
8.2.2 When the assembly can be 9.0 Quality Control. [Reserved]
Same as in Method 5, Section 8.1.3,
safely handled, wipe off all external 10.0 Calibration and Standardization
except the following: Using a tweezer or
particulate matter near the tip of the
clean disposable surgical gloves, place a The calibrations of the probe nozzle,
probe nozzle and place a cap over it to
labeled (identified) and weighed filter in prevent losing or gaining particulate pitot tube, metering system, temperature
the filter holder. Be sure that the filter matter. Do not cap off the probe tip sensors, and barometer are the same as
is properly centered and the gasket tightly while the sampling train is in Method 5, Sections 10.1 through 10.3,
properly placed so as not to allow the cooling down as this would create a 10.5, and 10.6, respectively.
sample gas stream to circumvent the vacuum in the filter holder, forcing
filter. Check filter for tears after 11.0 Analytical Procedure
condenser water backward.
assembly is completed. Mark the probe 8.2.3 Before moving the sample train Same as in Method 5, Section 11.0.
extension with heat resistant tape or by to the cleanup site, disconnect the filter Analytical data should be recorded on a
some other method to denote the proper holder-probe nozzle assembly from the form similar to that shown in Figure 5–
distance into the stack or duct for each probe extension; cap the open inlet of 6 of Method 5.
sampling point. Assemble the train as in the probe extension. Be careful not to
Figure 17–1, using a very light coat of 12.0 Data Analysis and Calculations.
lose any condensate, if present. Remove
silicone grease on all ground glass joints the umbilical cord from the condenser Same as in Method 5, Section 12.0.
and greasing only the outer portion (see outlet and cap the outlet. If a flexible
APTD–0576) to avoid possibility of 13.0 Method Performance. [Reserved]
line is used between the first impinger
contamination by the silicone grease. (or condenser) and the probe extension, 14.0 Pollution Prevention. [Reserved]
Place crushed ice around the impingers. disconnect the line at the probe 15.0 Waste Management. [Reserved]
8.1.4 Leak-Check Procedures. Same extension and let any condensed water
as in Method 5, Section 8.1.4, except or liquid drain into the impingers or 16.0 Alternative Procedures
that the filter holder is inserted into the condenser. Disconnect the probe Same as in Method 5, Section 16.0.
stack during the sampling train leak- extension from the condenser; cap the
check. To do this, plug the inlet to the probe extension outlet. After wiping off 17.0 References
probe nozzle with a material that will be the silicone grease, cap off the Same as in Method 5, Section 17.0,
able to withstand the stack temperature. condenser inlet. Ground glass stoppers, with the addition of the following:
Insert the filter holder into the stack and plastic caps, or serum caps (whichever
wait approximately 5 minutes (or 1. Vollaro, R.F. Recommended Procedure
are appropriate) may be used to close for Sample Traverses in Ducts Smaller than
longer, if necessary) to allow the system these openings. 12 Inches in Diameter. U.S. Environmental
to come to equilibrium with the 8.2.4 Transfer both the filter holder- Protection Agency, Emission Measurement
temperature of the stack gas stream. probe nozzle assembly and the Branch. Research Triangle Park, NC.
8.1.5 Sampling Train Operation. The condenser to the cleanup area. This area November 1976.
operation is the same as in Method 5. should be clean and protected from the BILLING CODE 6560–50–P

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18.0 Tables, Diagrams, Flowcharts, and Validation Data

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BILLING CODE 6560–50–C

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Method 18—Measurement of Gaseous 2.0 Summary of Method applicability of regulatory limitations
Organic Compound Emissions By Gas The major organic components of a prior to performing this test method.
Chromatography gas mixture are separated by gas The analyzer users manual should be
chromatography (GC) and individually consulted for specific precautions to be
Note: This method is not inclusive with taken with regard to the analytical
respect to specifications (e.g., equipment and quantified by flame ionization,
supplies) and procedures (e.g., sampling and photoionization, electron capture, or procedure.
analytical) essential to its performance. Some other appropriate detection principles. 6.0 Equipment and Supplies
material is incorporated by reference from The retention times of each separated
other methods in this part. Therefore, to 6.1 Equipment needed for the
component are compared with those of
obtain reliable results, persons using this presurvey sampling procedure can be
known compounds under identical
method should have a thorough knowledge found in Section 16.1.1.
conditions. Therefore, the analyst
of at least the following additional test 6.2 Equipment needed for the
methods: Method 1, Method 2, Method 3. confirms the identity and approximate
integrated bag sampling and analysis
concentrations of the organic emission
Note: This method should not be attempted procedure can be found in Section
components beforehand. With this
by persons unfamiliar with the performance 8.2.1.1.1.
information, the analyst then prepares 6.3 Equipment needed for direct
characteristics of gas chromatography, nor by
those persons who are unfamiliar with source or purchases commercially available interface sampling and analysis can be
sampling. Particular care should be exercised standard mixtures to calibrate the GC found in Section 8.2.2.1.
in the area of safety concerning choice of under conditions identical to those of 6.4 Equipment needed for the
equipment and operation in potentially the samples. The analyst also dilution interface sampling and analysis
explosive atmospheres. determines the need for sample dilution can be found in Section 8.2.3.1.
to avoid detector saturation, gas stream 6.5 Equipment needed for adsorbent
1.0 Scope and Application filtration to eliminate particulate matter, tube sampling and analysis can be
1.1 Analyte. Total gaseous organic and prevention of moisture found in Section 8.2.4.1.
compounds. condensation.
7.0 Reagents and Standards
1.2 Applicability. 3.0 Definitions. [Reserved]
7.1 Reagents needed for the
1.2.1 This method is designed to 4.0 Interferences presurvey sampling procedure can be
measure gaseous organics emitted from 4.1 Resolution interferences that found in Section 16.1.2.
an industrial source. While designed for may occur can be eliminated by 7.2 Quality Assurance Audit
ppm level sources, some detectors are appropriate GC column and detector Samples. When making compliance
quite capable of detecting compounds at choice or by shifting the retention times determinations, and upon availability,
ambient levels, e.g., ECD, ELCD, and through changes in the column flow rate an audit sample may be obtained from
helium ionization detectors. Some other and the use of temperature the appropriate EPA Regional Office or
types of detectors are evolving such that programming. from the responsible enforcement
the sensitivity and applicability may 4.2 The analytical system is authority.
well be in the ppb range in only a few demonstrated to be essentially free from Note: The responsible enforcement autority
years. contaminants by periodically analyzing should be notified at least 30 days prior to
1.2.2 This method will not blanks that consist of hydrocarbon-free the test date to allow sufficient time for
determine compounds that (1) are air or nitrogen. sample delivery.
polymeric (high molecular weight), (2) 4.3 Sample cross-contamination that
8.0 Sample Collection, Preservation,
can polymerize before analysis, or (3) occurs when high-level and low-level
Storage, and Transport
have very low vapor pressures at stack samples or standards are analyzed
or instrument conditions. alternately is best dealt with by 8.2 Final Sampling and Analysis
thorough purging of the GC sample loop Procedure. Considering safety (flame
1.3 Range. The lower range of this
between samples. hazards) and the source conditions,
method is determined by the sampling
4.4 To assure consistent detector select an appropriate sampling and
system; adsorbents may be used to
response, calibration gases are analysis procedure (Section 8.2.1, 8.2.2,
concentrate the sample, thus lowering
contained in dry air. To adjust gaseous 8.2.3 or 8.2.4). In situations where a
the limit of detection below the 1 part
organic concentrations when water hydrogen flame is a hazard and no
per million (ppm) typically achievable
vapor is present in the sample, water intrinsically safe GC is suitable, use the
with direct interface or bag sampling.
vapor concentrations are determined for flexible bag collection technique or an
The upper limit is governed by GC
those samples, and a correction factor is adsorption technique.
detector saturation or column 8.2.1 Integrated Bag Sampling and
applied.
overloading; the upper range can be 4.5 The gas chromatograph run time Analysis.
extended by dilution of sample with an must be sufficient to clear all eluting 8.2.1.1 Evacuated Container
inert gas or by using smaller volume gas peaks from the column before Sampling Procedure. In this procedure,
sampling loops. The upper limit can proceeding to the next run (in order to the bags are filled by evacuating the
also be governed by condensation of prevent sample carryover). rigid air-tight container holding the
higher boiling compounds. bags. Use a field sample data sheet as
1.4 Sensitivity. The sensitivity limit 5.0 Safety shown in Figure 18–10. Collect
for a compound is defined as the 5.1 Disclaimer. This method may triplicate samples from each sample
minimum detectable concentration of involve hazardous materials, operations, location.
that compound, or the concentration and equipment. This test method may 8.2.1.1.1 Apparatus.
that produces a signal-to-noise ratio of not address all of the safety problems 8.2.1.1.1.1 Probe. Stainless steel,
three to one. The minimum detectable associated with its use. It is the Pyrex glass, or Teflon tubing probe,
concentration is determined during the responsibility of the user of this test according to the duct temperature, with
presurvey calibration for each method to establish appropriate safety Teflon tubing of sufficient length to
compound. and health practices and determine the connect to the sample bag. Use stainless

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steel or Teflon unions to connect probe pumps, heated probes, or other flame same manner. Prepare a calibration
and sample line. producing equipment. curve as described in Section 10.2.
8.2.1.1.1.2 Quick Connects. Male (2) 8.2.1.4 Other Modified Bag 8.2.1.5.2.2 Analyze the two field
and female (2) of stainless steel Sampling Procedures. In the event that audit samples as described in Section
construction. condensation is observed in the bag 9.2 by connecting each Tedlar bag
8.2.1.1.1.3 Needle Valve. To control while collecting the sample and a direct containing an audit gas mixture to the
gas flow. interface system cannot be used, heat sampling valve. Calculate the results;
8.2.1.1.1.4 Pump. Leakless Teflon- the bag during collection, and maintain record and report the data to the audit
coated diaphragm-type pump or it at a suitably elevated temperature supervisor.
equivalent. To deliver at least 1 liter/ during all subsequent operations. (Note: 8.2.1.5.2.3 Analyze the three source
min. Take care to leak-check the system prior gas samples by connecting each bag to
8.2.1.1.1.5 Charcoal Adsorption to the dilutions so as not to create a the sampling valve with a piece of
Tube. Tube filled with activated potentially explosive atmosphere.) As Teflon tubing identified with that bag.
charcoal, with glass wool plugs at each an alternative, collect the sample gas, Analyze each bag sample three times.
end, to adsorb organic vapors. and simultaneously dilute it in the Record the data in Figure 18–11. If
8.2.1.1.1.6 Flowmeter. 0 to 500-ml certain items do not apply, use the
Tedlar bag.
flow range; with manufacturer’s notation ‘‘N.A.’’ If the bag has been
calibration curve. 8.2.1.4.1 First Alternative Procedure.
Heat the box containing the sample bag maintained at an elevated temperature
8.2.1.1.2 Sampling Procedure. To as described in Section 8.2.1.4,
obtain a sample, assemble the sample to 120 °C (±5 °C). Then transport the bag
as rapidly as possible to the analytical determine the stack gas water content by
train as shown in Figure 18–9. Leak- Method 4. After all samples have been
check both the bag and the container. area while maintaining the heating, or
cover the box with an insulating analyzed, repeat the analysis of the mid-
Connect the vacuum line from the level calibration gas for each compound.
needle valve to the Teflon sample line blanket. In the analytical area, keep the
box heated to 120 °C (±5 °C) until Compare the average response factor of
from the probe. Place the end of the the pre- and post-test analysis for each
probe at the centroid of the stack or at analysis. Be sure that the method of
compound. If they differ by >5percent,
a point no closer to the walls than 1 m, heating the box and the control for the
analyze the other calibration gas levels
and start the pump. Set the flow rate so heating circuit are compatible with the
for that compound, and prepare a
that the final volume of the sample is safety restrictions required in each area.
calibration curve using all the pre- and
approximately 80 percent of the bag 8.2.1.4.2 Second Alternative
post-test calibration gas mixture values.
capacity. After allowing sufficient time Procedure. Prefill the Tedlar bag with a
If the two response factor averages (pre-
to purge the line several times, connect known quantity of inert gas. Meter the
and post-test) differ by less than 5
the vacuum line to the bag, and inert gas into the bag according to the percent from their mean value, the tester
evacuate until the rotameter indicates procedure for the preparation of gas has the option of using only the pre-test
no flow. Then position the sample and concentration standards of volatile calibration curve to generate the
vacuum lines for sampling, and begin liquid materials (Section 10.1.2.2), but concentration values.
the actual sampling, keeping the rate eliminate the midget impinger section. 8.2.1.6 Determination of Bag Water
proportional to the stack velocity. As a Take the partly filled bag to the source, Vapor Content. Measure the ambient
precaution, direct the gas exiting the and meter the source gas into the bag temperature and barometric pressure
rotameter away from sampling through heated sampling lines and a near the bag. From a water saturation
personnel. At the end of the sample heated flowmeter, or Teflon positive vapor pressure table, determine and
period, shut off the pump, disconnect displacement pump. Verify the dilution record the water vapor content of the
the sample line from the bag, and factors before sampling each bag bag as a decimal figure. (Assume the
disconnect the vacuum line from the through dilution and analysis of gases of relative humidity to be 100 percent
bag container. Record the source known concentration. unless a lesser value is known.) If the
temperature, barometric pressure, 8.2.1.5 Analysis of Bag Samples. bag has been maintained at an elevated
ambient temperature, sampling flow 8.2.1.5.1 Apparatus. Same as Section temperature as described in Section
rate, and initial and final sampling time 8.1. A minimum of three gas standards 8.2.1.4, determine the stack gas water
on the data sheet shown in Figure 18– are required. content by Method 4.
10. Protect the Tedlar bag and its 8.2.1.5.2 Procedure. 8.2.1.7 Audit Gas Analysis.
container from sunlight. Record the time 8.2.1.5.2.1 Establish proper GC Immediately prior to the analysis of the
lapsed between sample collection and operating conditions as described in stack gas samples, perform audit
analysis, and then conduct the recovery Section 10.2, and record all data listed analyses as described in Section 9.2.
procedure in Section 8.4.2. in Figure 18–7. Prepare the GC so that 8.2.1.8 Emission Calculations. From
8.2.1.2 Direct Pump Sampling gas can be drawn through the sample the calibration curve described in
Procedure. Follow 8.2.1.1, except place valve. Flush the sample loop with Section 8.2.1.5, select the value of Cs
the pump and needle valve between the calibration gas mixture, and activate the that corresponds to the peak area.
probe and the bag. Use a pump and valve (sample pressure at the inlet to the Calculate the concentration Cc in ppm,
needle valve constructed of inert GC introduction valve should be similar dry basis, of each organic in the sample
material not affected by the stack gas. during calibration as during actual using Equation 18–5 in Section 12.6.
Leak-check the system, and then purge sample analysis). Obtain at least three 8.2.2 Direct Interface Sampling and
with stack gas before connecting to the chromatograms for the mixture. The Analysis Procedure. The direct interface
previously evacuated bag. results are acceptable when the peak procedure can be used provided that the
8.2.1.3 Explosion Risk Area Bag areas for the three injections agree to moisture content of the gas does not
Sampling Procedure. Follow 8.2.1.1 within 5 percent of their average. If they interfere with the analysis procedure,
except replace the pump with another do not agree, run additional samples or the physical requirements of the
evacuated can (see Figure 18–9a). Use correct the analytical techniques until equipment can be met at the site, and
this method whenever there is a this requirement is met. Then analyze the source gas concentration falls within
possibility of an explosion due to the other two calibration mixtures in the the linear range of the detector. Adhere

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to all safety requirements with this readout device, control the heating to pump of larger capacity is also required,
method. maintain a temperature greater than 110 and this pump must be heated and
8.2.2.1 Apparatus. °C. Conduct a 3-point calibration of the placed in the system between the
8.2.2.1.1 Probe. Constructed of GC by analyzing each gas mixture in sample line and the dilution apparatus.
stainless steel, Pyrex glass, or Teflon triplicate. Generate a calibration curve. 8.2.3.1 Apparatus. The equipment
tubing as dictated by duct temperature Place the inlet of the probe at the required in addition to that specified for
and reactivity of target compounds. A centroid of the duct, or at a point no the direct interface system is as follows:
filter or glass wool plug may be needed closer to the walls than 1 m, and draw 8.2.3.1.1 Sample Pump. Leakless
if particulate is present in the stack gas. source gas into the probe, heated line, Teflon-coated diaphragm-type that can
If necessary, heat the probe with heating and sample loop. After thorough withstand being heated to 120°C and
tape or a special heating unit capable of flushing, analyze the stack gas sample deliver 1.5 liters/minute.
maintaining a temperature greater than using the same conditions as for the 8.2.3.1.2 Dilution Pumps. Two
110 °C. calibration gas mixture. For each run, Model A–150 Komhyr Teflon positive
8.2.2.1.2 Sample Lines. 6.4-mm OD sample, analyze, and record five displacement type delivering 150 cc/
(or other diameter as needed) Teflon consecutive samples. A test consists of minute, or equivalent. As an option,
lines, heat-traced to prevent three runs (five samples per run times calibrated flowmeters can be used in
condensation of material (greater than three runs, for a total of fifteen samples). conjunction with Teflon-coated
110 °C). After all samples have been analyzed, diaphragm pumps.
8.2.2.1.3 Quick Connects. To repeat the analysis of the mid-level 8.2.3.1.3 Valves. Two Teflon three-
connect sample line to gas sampling calibration gas for each compound. For way valves, suitable for connecting to
valve on GC instrument and to pump each calibration standard, compare the Teflon tubing.
unit used to withdraw source gas. Use 8.2.3.1.4 Flowmeters. Two, for
pre- and post-test average response
a quick connect or equivalent on the measurement of diluent gas.
factors (RF) for each compound. If the 8.2.3.1.5 Diluent Gas with Cylinders
cylinder or bag containing calibration two calibration RF values (pre- and
gas to allow connection of the and Regulators. Gas can be nitrogen or
post-analysis) differ by more than 5 clean dry air, depending on the nature
calibration gas to the gas sampling percent from their mean value, then
valve. of the source gases.
analyze the other calibration gas levels 8.2.3.1.6 Heated Box. Suitable for
8.2.2.1.4 Thermocouple Readout for that compound and determine the
Device. Potentiometer or digital being heated to 120 °C, to contain the
stack gas sample concentrations by three pumps, three-way valves, and
thermometer, to measure source comparison to both calibration curves
temperature and probe temperature. associated connections. The box should
(this is done by preparing a calibration be equipped with quick connect fittings
8.2.2.1.5 Heated Gas Sampling curve using all the pre and post-test
Valve. Of two-position, six-port design, to facilitate connection of: (1) the heated
calibration gas mixture values). If the sample line from the probe, (2) the gas
to allow sample loop to be purged with two calibration RF values differ by less
source gas or to direct source gas into sampling valve, (3) the calibration gas
than 5 percent from their mean value, mixtures, and (4) diluent gas lines. A
the GC instrument. the tester has the option of using only
8.2.2.1.6 Needle Valve. To control schematic diagram of the components
the pre-test calibration curve to generate and connections is shown in Figure 18–
gas sampling rate from the source. the concentration values. Record this
8.2.2.1.7 Pump. Leakless Teflon- 13. The heated box shown in Figure 18–
calibration data and the other required 13 is designed to receive a heated line
coated diaphragm-type pump or
data on the data sheet shown in Figure from the probe. An optional design is to
equivalent, capable of at least 1 liter/
18–11, deleting the dilution gas build a probe unit that attaches directly
minute sampling rate.
information. to the heated box. In this way, the
8.2.2.1.8 Flowmeter. Of suitable
range to measure sampling rate. Note: Take care to draw all samples, heated box contains the controls for the
8.2.2.1.9 Charcoal Adsorber. To calibration mixtures, and audits through the probe heaters, or, if the box is placed
adsorb organic vapor vented from the sample loop at the same pressure. against the duct being sampled, it may
source to prevent exposure of personnel 8.2.2.3 Determination of Stack Gas be possible to eliminate the probe
to source gas. Moisture Content. Use Method 4 to heaters. In either case, a heated Teflon
8.2.2.1.10 Gas Cylinders. Carrier gas, measure the stack gas moisture content. line is used to connect the heated box
oxygen and fuel as needed to run GC 8.2.2.4 Quality Assurance. Same as to the gas sampling valve on the
and detector. Section 8.2.1.7. Introduce the audit chromatograph.
8.2.2.1.11 Gas Chromatograph. gases in the sample line immediately Note: Care must be taken to leak-check the
Capable of being moved into the field, following the probe. system prior to the dilutions so as not to
with detector, heated gas sampling 8.2.2.5 Emission Calculations. Same create a potentially explosive atmosphere.
valve, column required to complete as Section 8.2.1.8. 8.2.3.2 Procedure.
separation of desired components, and 8.2.3 Dilution Interface Sampling 8.2.3.2.1 Assemble the apparatus by
option for temperature programming. and Analysis Procedure. Source samples connecting the heated box, shown in
8.2.2.1.12 Recorder/Integrator. To that contain a high concentration of Figure 18–13, between the heated
record results. organic materials may require dilution sample line from the probe and the gas
8.2.2.2 Procedure. Calibrate the GC prior to analysis to prevent saturating sampling valve on the chromatograph.
using the procedures in Section the GC detector. The apparatus required Vent the source gas from the gas
8.2.1.5.2.1. To obtain a stack gas sample, for this direct interface procedure is sampling valve directly to the charcoal
assemble the sampling system as shown basically the same as that described in filter, eliminating the pump and
in Figure 18–12. Make sure all the Section 8.2.2, except a dilution rotameter. Heat the sample probe,
connections are tight. Turn on the probe system is added between the heated sample line, and heated box. Insert the
and sample line heaters. As the sample line and the gas sampling valve. probe and source thermocouple at the
temperature of the probe and heated The apparatus is arranged so that either centroid of the duct, or to a point no
line approaches the target temperature a 10:1 or 100:1 dilution of the source gas closer to the walls than 1 m. Measure
as indicated on the thermocouple can be directed to the chromatograph. A the source temperature, and adjust all

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heating units to a temperature 0 to 3°C with a heating system if water percent, the adsorptive capacity may be
above this temperature. If this condensation is a problem, and a filter severely reduced. Operate the gas
temperature is above the safe operating (either in-stack or out-of-stack, heated to chromatograph according to the
temperature of the Teflon components, stack temperature) to remove particulate manufacturer’s instructions. After
adjust the heating to maintain a matter. In most instances, a plug of glass establishing optimum conditions, verify
temperature high enough to prevent wool is a satisfactory filter. and document these conditions during
condensation of water and organic 8.2.4.1.2 Flexible Tubing. To all operations. Calibrate the instrument.
compounds (greater than 110 °C). connect probe to adsorption tubes. Use Analyze the audit samples (see Section
Calibrate the GC through the dilution a material that exhibits minimal sample 16.1.4.3), then the emission samples.
system by following the procedures in adsorption. 8.2.4.3 Standards and Calibration. If
Section 8.2.1.5.2.1. Determine the 8.2.4.1.3 Leakless Sample Pump. using thermal desorption, obtain
concentration of the diluted calibration Flow controlled, constant rate pump, calibration gases using the procedures
gas using the dilution factor and the with a set of limiting (sonic) orifices. in Section 10.1. If using solvent
certified concentration of the calibration 8.2.4.1.4 Bubble-Tube Flowmeter. extraction, prepare liquid standards in
gas. Record the pertinent data on the Volume accuracy within 1 percent, to the desorption solvent. Use a minimum
data sheet shown in Figure 18–11. calibrate pump. of three different standards; select the
8.2.3.2.2 Once the dilution system 8.2.4.1.5 Stopwatch. To time concentrations to bracket the expected
and GC operations are satisfactory, sampling and pump rate calibration. average sample concentration. Perform
proceed with the analysis of source gas, 8.2.4.1.6 Adsorption Tubes. the calibration before and after each
maintaining the same dilution settings Precleaned adsorbent, with mass of day’s sample analyses using the
as used for the standards. adsorbent to be determined by procedures in Section 8.2.1.5.2.1.
8.2.3.2.3 Analyze the audit samples calculating breakthrough volume and 8.2.4.4 Quality Assurance.
using either the dilution system, or expected concentration in the stack. 8.2.4.4.1 Determine the recovery
directly connect to the gas sampling 8.2.4.1.7 Barometer. Accurate to 5 efficiency of the pollutants of interest
valve as required. Record all data and mm Hg, to measure atmospheric according to Section 8.4.3.
report the results to the audit pressure during sampling and pump 8.2.4.4.2 Determination of Sample
supervisor. calibration. Collection Efficiency (Optional). If
8.2.3.3 Determination of Stack Gas 8.2.4.1.8 Rotameter. O to 100 cc/ sample breakthrough is thought to be a
Moisture Content. Same as Section min, to detect changes in flow rate problem, a routine procedure for
8.2.2.3. during sampling. determining breakthrough is to analyze
8.2.3.4 Quality Assurance. Same as 8.2.4.2 Sampling and Analysis. the primary and backup portions of the
Section 8.2.2.4. 8.2.4.2.1 Calibrate the pump and adsorption tubes separately. If the
8.2.3.5 Emission Calculations. Same limiting orifice flow rate through backup portion exceeds 10 percent of
as section 8.2.2.5, with the dilution adsorption tubes with the bubble tube the total amount (primary and back-up),
factor applied. flowmeter before sampling. The sample it is usually a sign of sample
8.2.4 Adsorption Tube Procedure. system can be operated as a breakthrough. For the purposes of this
Any commercially available adsorbent ‘‘recirculating loop’’ for this operation. method, only the recovery efficiency
is allowed for the purposes of this Record the ambient temperature and value (Section 8.4.3) is used to
method, as long as the recovery study barometric pressure. Then, during determine the appropriateness of the
criteria in Section 8.4.3 are met. Help in sampling, use the rotameter to verify sampling and analytical procedure.
choosing the adsorbent may be found by that the pump and orifice sampling rate 8.2.4.4.3 Volume Flow Rate Checks.
calling the distributor, or the tester may remains constant. Perform this check immediately after
refer to National Institute for 8.2.4.2.2 Use a sample probe, if sampling with all sampling train
Occupational Safety and Health required, to obtain the sample at the components in place. Use the bubble-
(NIOSH) methods for the particular centroid of the duct, or at a point no tube flowmeter to measure the pump
organics to be sampled. For some closer to the walls than 1 m. Minimize volume flow rate with the orifice used
adsorbents, the principal interferent will the length of flexible tubing between the in the test sampling, and record the
be water vapor. If water vapor is thought probe and adsorption tubes. Several result. If it has changed by more than 5
to be a problem, the tester may place a adsorption tubes can be connected in but less than 20 percent, calculate an
midget impinger in an ice bath before series, if the extra adsorptive capacity is average flow rate for the test. If the flow
the adsorbent tubes. If this option is needed. Adsorption tubes should be rate has changed by more than 20
chosen, the water catch in the midget maintained vertically during the test in percent, recalibrate the pump and repeat
impinger shall be analyzed for the target order to prevent channeling. Provide the the sampling.
compounds. Also, the spike for the gas sample to the sample system at a 8.2.4.4.4 Calculations. Correct all
recovery study (in Section 8.4.3) shall pressure sufficient for the limiting sample volumes to standard conditions.
be conducted in both the midget orifice to function as a sonic orifice. If a sample dilution system has been
impinger and the adsorbent tubes. The Record the total time and sample flow used, multiply the results by the
combined recovery (add the recovered rate (or the number of pump strokes), appropriate dilution ratio. Correct all
amount in the impinger and the the barometric pressure, and ambient results according to the applicable
adsorbent tubes to calculate R) shall temperature. Obtain a total sample procedure in Section 8.4.3. Report
then meet the criteria in Section 8.4.3. volume commensurate with the results as ppm by volume, dry basis.
Note: Post-test leak-checks are not allowed expected concentration(s) of the volatile 8.3 Reporting of Results. At the
for this technique since this can result in organic(s) present, and recommended completion of the field analysis portion
sample contamination. sample loading factors (weight sample of the study, ensure that the data sheets
8.2.4.1 Additional Apparatus. The per weight adsorption media). shown in Figure 18–11 have been
following items (or equivalent) are Laboratory tests prior to actual sampling completed. Summarize this data on the
suggested. may be necessary to predetermine this data sheets shown in Figure 18–15.
8.2.4.1.1 Probe. Borosilicate glass or volume. If water vapor is present in the 8.4 Recovery Study. After
stainless steel, approximately 6-mm ID, sample at concentrations above 2 to 3 conducting the presurvey and

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identifying all of the pollutants of concentration, in ppm, of each spiked the outside edge of the other. One of the
interest, conduct the appropriate compound in the bag shall be 40 to 60 sampling trains shall be designated the
recovery study during the test based on percent of the average concentration spiked train and the other the unspiked
the sampling system chosen for the measured in the three bag samples. If a train. Spike all of the compounds of
compounds of interest. target compound was not detected in interest (in gaseous or liquid form) onto
8.4.1 Recovery Study for Direct the bag samples, the concentration of the adsorbent tube(s) in the spiked train
Interface or Dilution Interface Sampling. that compound to be spiked shall be 5 before sampling. The mass of each
If the procedures in Section 8.2.2 or times the limit of detection for that spiked compound shall be 40 to 60
8.2.3 are to be used to analyze the stack compound. Store the spiked bag for the percent of the mass expected to be
gas, conduct the calibration procedure same period of time as the bag samples collected with the unspiked train.
as stated in Section 8.2.2.2 or 8.2.3.2, as collected in the field. After the Sample the stack gas into the two trains
appropriate. Upon successful appropriate storage time has passed, simultaneously. Analyze the adsorbents
completion of the appropriate analyze the spiked bag three times. from the two trains utilizing identical
calibration procedure, attach the mid- Calculate the average fraction recovered analytical procedures and
level calibration gas for at least one (R) of each spiked target compound with instrumentation. Determine the fraction
target compound to the inlet of the the equation in Section 12.7. of spiked compound recovered (R) using
probe or as close as possible to the inlet 8.4.2.2 For the bag sampling the equations in Section 12.9.
of the probe, but before the filter. Repeat technique to be considered valid for a
compound, 0.70 ≤ R ≤ 1.30. If the R 8.4.3.1 Repeat the procedure in
the calibration procedure by sampling
value does not meet this criterion for a Section 8.4.3 twice more, for a total of
and analyzing the mid-level calibration
target compound, the sampling three runs. In order for the adsorbent
gas through the entire sampling and
technique is not acceptable for that tube sampling and analytical procedure
analytical system in triplicate. The
compound, and therefore another to be acceptable for a compound,
mean of the calibration gas response
sampling technique shall be evaluated 0.70≤R≤1.30 (R in this case is the
sampled through the probe shall be
for acceptance (by repeating the average of three runs). If the average R
within 10 percent of the analyzer
recovery study with another sampling value does not meet this criterion for a
response. If the difference in the two
technique). Report the R value in the target compound, the sampling
means is greater than 10 percent, check
test report and correct all field technique is not acceptable for that
for leaks throughout the sampling
measurements with the calculated R compound, and therefore another
system and repeat the analysis of the
value for that compound by using the sampling technique shall be evaluated
standard through the sampling system
equation in Section 12.8. for acceptance (by repeating the
until this criterion is met.
8.4.2 Recovery Study for Bag 8.4.3 Recovery Study for Adsorption recovery study with another sampling
Sampling. Tube Sampling. If following the technique). Report the R value in the
8.4.2.1 Follow the procedures for the adsorption tube procedure in Section test report and correct all field
bag sampling and analysis in Section 8.2.4, conduct a recovery study of the measurements with the calculated R
8.2.1. After analyzing all three bag compounds of interest during the actual value for that compound by using the
samples, choose one of the bag samples field test. Set up two identical sampling equation in Section 12.8.
and tag this bag as the spiked bag. Spike trains. Collocate the two sampling 9.0 Quality Control
the chosen bag sample with a known probes in the stack. The probes shall be
mixture (gaseous or liquid) of all of the placed in the same horizontal plane, 9.1 Miscellaneous Quality Control
target pollutants. The theoretical where the first probe tip is 2.5 cm from Measures

Section Quality control measure Effect

8.4.1 .......................................... Recovery study for direct interface or dilution Ensure that there are no significant leaks in the sampling sys-
interface sampling. tem.
8.4.2 .......................................... Recovery study for bag sampling .................... Demonstrate that proper sampling/analysis procedures were
selected.
8.4.3 .......................................... Recovery study for adsorption tube sampling Demonstrate that proper sampling/analysis procedures were
selected.

9.2 Quality Assurance for Laboratory 10.0 Calibration and Standardization. multi-level calibration gas standards.
Procedures. Immediately after the Prepare or obtain enough calibration
preparation of the calibration curves, 10.1 Calibration Standards. Obtain standards so that there are three
the analysis audit described in 40 CFR calibration gas standards for each target different concentrations of each organic
Part 61, Appendix C, Procedure 2: compound to be analyzed. Commercial compound expected to be measured in
‘‘Procedure for Field Auditing GC cylinder gases certified by the the source sample. For each organic
Analysis,’’ should be performed if audit manufacturer to be accurate to within 1 compound, select those concentrations
materials are available. The information percent of the certified label value are that bracket the concentrations expected
required to document the analysis of the preferable, although cylinder gases in the source samples. A calibration
audit samples has been included on the certified by the manufacturer to 2 standard may contain more than one
example data sheets shown in Figures percent accuracy are allowed. Another organic compound. If samples are
18–3 and 18–7. The audit analyses option allowed by this method is for the
collected in adsorbent tubes and
should agree with the certified audit tester to obtain high concentration
extracted using solvent extraction,
concentrations within 10 percent. Audit certified cylinder gases and then use a
prepare or obtain standards in the same
sample results shall be submitted dilution system meeting the
solvent used for the sample extraction
according to directions provided with requirements of Test Method 205, 40
procedure. Verify the stability of all
the audit samples. CFR Part 51, Appendix M to make

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standards for the time periods they are times against those of the calibration mu = Total mass of compound measured
used. samples that contain the components on adsorbent with unspiked train
10.2 Preparation of Calibration expected to be in the stream. If any (µg).
Curves. compounds cannot be identified with mv = Mass per volume of spiked
10.2.1 Establish proper GC certainty by this procedure, identify compound measured (µg/L).
conditions, then flush the sampling loop them by other means such as GC/mass Pi = Barometric or absolute sample loop
for 30 seconds. Allow the sample loop spectroscopy (GC/MS) or GC/infrared pressure at time of sample analysis,
pressure to equilibrate to atmospheric techniques. A GC/MS system is mm Hg.
pressure, and activate the injection recommended. Pm = Absolute pressure of dry gas meter,
valve. Record the standard 11.1.1.4.2 Use the GC conditions mm Hg.
concentration, attenuator factor, determined by the procedure of Section Pr = Reference pressure, the barometric
injection time, chart speed, retention 11.1.1.2 for the first injection. Vary the pressure or absolute sample loop
time, peak area, sample loop GC parameters during subsequent pressure recorded during
temperature, column temperature, and injections to determine the optimum calibration, mm Hg.
carrier gas flow rate. Analyze each settings. Once the optimum settings Ps = Absolute pressure of syringe before
standard in triplicate. have been determined, perform repeat injection, mm Hg.
10.2.2 Repeat this procedure for injections of the sample to determine qc = Flow rate of the calibration gas to
each standard. Prepare a graphical plot the retention time of each compound. be diluted.
of concentration (Cs) versus the To inject a sample, draw sample qc1 = Flow rate of the calibration gas to
calibration area values. Perform a through the loop at a constant rate (100 be diluted in stage 1.
qc2 = Flow rate of the calibration gas to
regression analysis, and draw the least ml/min for 30 seconds). Be careful not
be diluted in stage 2.
square line. to pressurize the gas in the loop. Turn
qd = Diluent gas flow rate.
off the pump and allow the gas in the qd1 = Flow rate of diluent gas in stage
11.0 Analytical Procedures
sample loop to come to ambient 1.
11.1 Analysis Development pressure. Activate the sample valve, and qd2 = Flow rate of diluent gas in stage
11.1.1 Selection of GC Parameters record injection time, loop temperature, 2.
11.1.1.1 Column Choice. Based on column temperature, carrier flow rate, s = Theoretical concentration (ppm) of
the initial contact with plant personnel chart speed, and attenuator setting. spiked target compound in the bag.
concerning the plant process and the Calculate the retention time of each S = Theoretical mass of compound
anticipated emissions, choose a column peak using the distance from injection spiked onto adsorbent in spiked
that provides good resolution and rapid to the peak maximum divided by the train (µg).
analysis time. The choice of an chart speed. Retention times should be t = Measured average concentration
appropriate column can be aided by a repeatable within 0.5 seconds. (ppm) of target compound and
literature search, contact with 11.1.1.4.3 If the concentrations are source sample (analysis results
manufacturers of GC columns, and too high for appropriate detector subsequent to bag spiking)
discussion with personnel at the response, a smaller sample loop or Ti = Sample loop temperature at the
emission source. dilutions may be used for gas samples, time of sample analysis, °K.
Note: Most column manufacturers keep and, for liquid samples, dilution with Tm = Absolute temperature of dry gas
excellent records on their products. Their solvent is appropriate. Use the standard meter, °K.
technical service departments may be able to curves (Section 10.2) to obtain an Ts = Absolute temperature of syringe
recommend appropriate columns and estimate of the concentrations. before injection, °K.
detector type for separating the anticipated u = Source sample average
11.1.1.4.4 Identify all peaks by
compounds, and they may be able to provide
comparing the known retention times of concentration (ppm) of target
information on interferences, optimum
operating conditions, and column compounds expected to be in the compound in the bag (analysis
limitations. Plants with analytical retention times of peaks in the sample. results before bag spiking).
laboratories may be able to provide Identify any remaining unidentified Vm = Gas volume indicated by dry gas
information on their analytical procedures. peaks which have areas larger than 5 meter, liters.
11.1.1.2 Preliminary GC Adjustment. percent of the total using a GC/MS, or vs = volume of stack gas sampled with
Using the standards and column estimation of possible compounds by spiked train (L).
obtained in Section 11.1.1.1, perform their retention times compared to vu = volume of stack gas sampled with
initial tests to determine appropriate GC known compounds, with confirmation unspiked train (L).
by further GC analysis. X = Mole or volume fraction of the
conditions that provide good resolution
organic in the calibration gas to be
and minimum analysis time for the 12.0 Data Analysis and Calculations diluted.
compounds of interest.
12.1 Nomenclature. Y = Dry gas meter calibration factor,
11.1.1.3 Preparation of Presurvey
dimensionless.
Samples. If the samples were collected Bws = Water vapor content of the bag
µl = Liquid organic density as
on an adsorbent, extract the sample as sample or stack gas, proportion by
determined, g/ml.
recommended by the manufacturer for volume.
removal of the compounds with a Cs = Concentration of the organic from 24.055 = Ideal gas molar volume at 293
solvent suitable to the type of GC the calibration curve, ppm. °K and 760 mm Hg, liters/g-mole.
analysis. Prepare other samples in an Gv = Gas volume or organic compound 1000 = Conversion factor, ml/liter.
appropriate manner. injected, ml. 106 = Conversion to ppm.
11.1.1.4 Presurvey Sample Analysis. Lv = Liquid volume of organic injected, 12.2 Calculate the concentration, Cs,
11.1.1.4.1 Before analysis, heat the µl. in ppm using the following equation:
presurvey sample to the duct M = Molecular weight of organic, g/g-
temperature to vaporize any condensed mole.
Cs =
(
10 6 Xq c ) Eq. 18-1
material. Analyze the samples by the GC ms = Total mass of compound measured
procedure, and compare the retention on adsorbent with spiked train (µg). qc + qd

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12.3 Calculate the concentration, Cs, in ppm of the organic in the final gas mixture using the following equation:

 q c1   q c 2 
Cs = 10 6 X    Eq. 18-2
 q c1 + q d1   q c 2 + q d 2 
12.4 Calculate each organic standard concentration, Cs, in ppm using the following equation:

293 Ps
G v × 10 6
Ts 760
Cs = Eq. 18-3
293 Pm
Vm Y 1000
Tm 760
Ps Tm
G v × 10 3
Ts Pm
=
Vm Y
12.5 Calculate each organic standard concentration, Cs, in ppm using the following equation:

Lv
M
(
ρ 24.055 × 10 6 ) L vρTm
Cs = = 6.24 × 10 4 Eq. 18-4
293 Pm MV m YPm
Vm Y 1000
Tm 760
12.6 Calculate the concentration, Cc, in ppm, dry basis, of each organic is the sample using the following equation:

12.7 Calculate the average fraction recovered (R) of each spiked target compound using the following equation:

t−u
R= Eq. 18-6
s
12.8 Correct all field measurements with the calculated R value for that compound using the following equation:

Measured Concentration (ppm)
Reported Result = Eq. 18-7
R

12.9 Determine the mass per volume various sources, a specific precision (c) Recovery. After developing an
of spiked compound measured using the limit for the analysis of field samples is appropriate sampling and analytical
following equation: impractical. Precision in the range of 5 system for the pollutants of interest,
to 10 percent relative standard deviation conduct the procedure in Section 8.4.
ms m u (RSD) is typical for gas chromatographic Conduct the appropriate recovery study
mv = − Eq. 18-8
Vs Vu techniques, but an experienced GC in Section 8.4 at each sampling point
operator with a reliable instrument can where the method is being applied.
12.10 Calculate the fraction of Submit the data and results of the
readily achieve 5 percent RSD. For this
spiked compound recovered, R, using recovery procedure with the reporting of
method, the following combined GC/
the following equation: results under Section 8.3.
operator values are required.
m v × vs (a) Precision. Triplicate analyses of 14.0 Pollution Prevention. [Reserved]
R= Eq. 18-9 calibration standards fall within 5
S 15.0 Waste Management. [Reserved]
percent of their mean value.
13.0 Method Performance 16.0 Alternative Procedures
(b) Accuracy. Analysis results of
13.1 Since a potential sample may prepared audit samples are within 10 16.1 Optional Presurvey and
contain a variety of compounds from percent of preparation values. Presurvey Sampling.

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Note: Presurvey screening is optional. 16.1.1.15 Sample Flasks. For Purge the assembly with high-purity
Presurvey sampling should be conducted for presurvey samples, must have gas-tight nitrogen for 2 to 5 minutes. Close off the
sources where the target pollutants are not seals. stopcocks after purging to maintain a
known from previous tests and/or process 16.1.1.16 Adsorption Tubes. If slight positive nitrogen pressure. Secure
knowledge.
necessary, blank tubes filled with the stopcocks with tape. Presurvey
Perform a presurvey for each source to necessary adsorbent (charcoal, Tenax, samples can be obtained either by
be tested. Refer to Figure 18–1. Some of XAD–2, etc.) for presurvey samples. drawing the gases into the previously
the information can be collected from 16.1.1.17 Personnel Sampling Pump. evacuated flask or by drawing the gases
literature surveys and source personnel. Calibrated, for collecting adsorbent tube into and purging the flask with a rubber
Collect gas samples that can be analyzed presurvey samples. suction bulb.
to confirm the identities and 16.1.1.18 Dilution System. 16.1.3.1.1 Evacuated Flask
approximate concentrations of the Calibrated, the dilution system is to be Procedure. Use a high-vacuum pump to
organic emissions. constructed following the specifications evacuate the flask to the capacity of the
16.1.1 Apparatus. This apparatus list of an acceptable method. pump; then close off the stopcock
also applies to Sections 8.2 and 11. 16.1.1.19 Sample Probes. Pyrex or leading to the pump. Attach a 6-mm
16.1.1.1 Teflon Tubing. (Mention of stainless steel, of sufficient length to outside diameter (OD) glass tee to the
trade names or specific products does reach centroid of stack, or a point no flask inlet with a short piece of Teflon
not constitute endorsement by the U.S. closer to the walls than 1 m. tubing. Select a 6-mm OD borosilicate
Environmental Protection Agency.) 16.1.1.20 Barometer. To measure sampling probe, enlarged at one end to
Diameter and length determined by barometric pressure. a 12-mm OD and of sufficient length to
connection requirements of cylinder 16.1.2 Reagents. reach the centroid of the duct to be
regulators and the GC. Additional 16.1.2.1 Water. Deionized distilled. sampled. Insert a glass wool plug in the
tubing is necessary to connect the GC 16.1.2.2 Methylene chloride. enlarged end of the probe to remove
sample loop to the sample. 16.1.2.3 Calibration Gases. A series particulate matter. Attach the other end
16.1.1.2 Gas Chromatograph. GC of standards prepared for every of the probe to the tee with a short piece
with suitable detector, columns, compound of interest. of Teflon tubing. Connect a rubber
temperature-controlled sample loop and 16.1.2.4 Organic Compound suction bulb to the third leg of the tee.
valve assembly, and temperature Solutions. Pure (99.9 percent), or as Place the filter end of the probe at the
programmable oven, if necessary. The pure as can reasonably be obtained, centroid of the duct, and purge the
GC shall achieve sensitivity liquid samples of all the organic probe with the rubber suction bulb.
requirements for the compounds under compounds needed to prepare After the probe is completely purged
study. calibration standards. and filled with duct gases, open the
16.1.1.3 Pump. Capable of pumping 16.1.2.5 Extraction Solvents. For stopcock to the grab flask until the
100 ml/min. For flushing sample loop. extraction of adsorbent tube samples in pressure in the flask reaches duct
16.1.1.4 Flow Meter. To measure preparation for analysis. pressure. Close off the stopcock, and
flow rates. 16.1.2.6 Fuel. As recommended by remove the probe from the duct.
16.1.1.5 Regulators. Used on gas the manufacturer for operation of the Remove the tee from the flask and tape
cylinders for GC and for cylinder GC. the stopcocks to prevent leaks during
standards. 16.1.2.7 Carrier Gas. Hydrocarbon shipment. Measure and record the duct
16.1.1.6 Recorder. Recorder with free, as recommended by the temperature and pressure.
linear strip chart is minimum manufacturer for operation of the 16.1.3.1.2 Purged Flask Procedure.
acceptable. Integrator (optional) is detector and compatibility with the Attach one end of the sampling flask to
recommended. column. a rubber suction bulb. Attach the other
16.1.1.7 Syringes. 0.5-ml, 1.0- and 16.1.2.8 Zero Gas. Hydrocarbon free end to a 6-mm OD glass probe as
10-microliter size, calibrated, maximum air or nitrogen, to be used for dilutions, described in Section 8.3.3.1.1. Place the
accuracy (gas tight) for preparing blank preparation, and standard filter end of the probe at the centroid of
calibration standards. Other appropriate preparation. the duct, or at a point no closer to the
sizes can be used. 16.1.3 Sampling. walls than 1 m, and apply suction with
16.1.1.8 Tubing Fittings. To plumb 16.1.3.1 Collection of Samples with the bulb to completely purge the probe
GC and gas cylinders. Glass Sampling Flasks. Presurvey and flask. After the flask has been
16.1.1.9 Septa. For syringe samples may be collected in precleaned purged, close off the stopcock near the
injections. 250-ml double-ended glass sampling suction bulb, and then close off the
16.1.1.10 Glass Jars. If necessary, flasks. Teflon stopcocks, without grease, stopcock near the probe. Remove the
clean, colored glass jars with Teflon- are preferred. Flasks should be cleaned probe from the duct, and disconnect
lined lids for condensate sample as follows: Remove the stopcocks from both the probe and suction bulb. Tape
collection. Size depends on volume of both ends of the flasks, and wipe the the stopcocks to prevent leakage during
condensate. parts to remove any grease. Clean the shipment. Measure and record the duct
16.1.1.11 Soap Film Flowmeter. To stopcocks, barrels, and receivers with temperature and pressure.
determine flow rates. methylene chloride (or other non-target 16.1.3.2 Flexible Bag Procedure.
16.1.1.12 Tedlar Bags. 10- and 50- pollutant solvent, or heat and Tedlar or aluminized Mylar bags can
liter capacity, for preparation of humidified air). Clean all glass ports also be used to obtain the presurvey
standards. with a soap solution, then rinse with tap sample. Use new bags, and leak-check
16.1.1.13 Dry Gas Meter with and deionized distilled water. Place the them before field use. In addition, check
Temperature and Pressure Gauges. flask in a cool glass annealing furnace, the bag before use for contamination by
Accurate to ±2 percent, for preparation and apply heat up to 500 °C. Maintain filling it with nitrogen or air, and
of gas standards. at this temperature for 1 hour. After this analyzing the gas by GC at high
16.1.1.14 Midget Impinger/Hot Plate time period, shut off and open the sensitivity. Experience indicates that it
Assembly. For preparation of gas furnace to allow the flask to cool. Return is desirable to allow the inert gas to
standards. the stopcocks to the flask receivers. remain in the bag about 24 hours or

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longer to check for desorption of Environmental Science and Technology. 17. McNair Han Bunelli, E.J. Basic Gas
organics from the bag. Follow the leak- 5(12):1200–1222. 1971. Chromatography. Consolidated Printers.
check and sample collection procedures 4. Eggertsen, F.T., and F.M. Nelsen. Gas Berkeley. 1969.
Chromatographic Analysis of Engine Exhaust 18. Nelson, G.O. Controlled Test
given in Section 8.2.1. and Atmosphere. Analytical Chemistry.
16.1.3.3 Determination of Moisture Atmospheres, Principles and Techniques.
30(6): 1040–1043. 1958. Ann Arbor. Ann Arbor Science Publishers.
Content. For combustion or water- 5. Feairheller, W.R., P.J. Marn, D.H. Harris, 1971. 247 p.
controlled processes, obtain the and D.L. Harris. Technical Manual for 19. NIOSH Manual of Analytical Methods,
moisture content from plant personnel Process Sampling Strategies for Organic Volumes 1, 2, 3, 4, 5, 6, 7. U.S. Department
or by measurement during the Materials. U.S. Environmental Protection of Health and Human Services, National
presurvey. If the source is below 59°C, Agency. Research Triangle Park, N.C.
Institute for Occupational Safety and Health.
measure the wet bulb and dry bulb Publication No. EPA 600/2–76–122. April
Center for Disease Control. 4676 Columbia
1976. 172 p.
temperatures, and calculate the 6. Federal Register, 39 FR 9319–9323. Parkway, Cincinnati, Ohio 45226. April
moisture content using a psychrometric 1974. 1977—August 1981. May be available from
chart. At higher temperatures, use 7. Federal Register, 39 FR 32857–32860. the Superintendent of Documents,
Method 4 to determine the moisture 1974. Government Printing Office, Washington,
content. 8. Federal Register, 23069–23072 and D.C. 20402. Stock Number/Price:
16.1.4 Determination of Static 23076–23090. 1976. Volume 1—O17–033–00267–3/$13
Pressure. Obtain the static pressure from 9. Federal Register, 46569–46571. 1976. Volume 2—O17–033–00260–6/$11
the plant personnel or measurement. If 10. Federal Register, 41771–41776. 1977. Volume 3—O17–033–00261–4/$14
11. Fishbein, L. Chromatography of Volume 4—O17–033–00317–3/$7.25
a type S pitot tube and an inclined Environmental Hazards, Volume II. Elesevier Volume 5—O17–033–00349–1/$10
manometer are used, take care to align Scientific Publishing Company. New York, Volume 6—O17–033–00369–6/$9
the pitot tube 90° from the direction of N.Y. 1973. Volume 7—O17–033–00396–5/$7
the flow. Disconnect one of the tubes to 12. Hamersma, J.W., S.L. Reynolds, and Prices subject to change. Foreign orders add
the manometer, and read the static R.F. Maddalone. EPA/IERL-RTP Procedures 25 percent.
pressure; note whether the reading is Manual: Level 1 Environmental Assessment.
20. Schuetzle, D., T.J. Prater, and S.R.
positive or negative. U.S. Environmental Protection Agency.
Ruddell. Sampling and Analysis of Emissions
16.1.5 Collection of Presurvey Research Triangle Park, N.C. Publication No.
from Stationary Sources; I. Odor and Total
EPA 600/276–160a. June 1976. 130 p.
Samples with Adsorption Tube. Follow Hydrocarbons. Journal of the Air Pollution
13. Harris, J.C., M.J. Hayes, P.L. Levins, and
Section 8.2.4 for presurvey sampling. D.B. Lindsay. EPA/IERL-RTP Procedures for Control Association. 25(9): 925–932. 1975.
Level 2 Sampling and Analysis of Organic 21. Snyder, A.D., F.N. Hodgson, M.A.
17.0 References Kemmer and J.R. McKendree. Utility of Solid
Materials. U.S. Environmental Protection
1. American Society for Testing and Agency. Research Triangle Park, N.C. Sorbents for Sampling Organic Emissions
Materials. C1 Through C5 Hydrocarbons in Publication No. EPA 600/7–79–033. February from Stationary Sources. U.S. Environmental
the Atmosphere by Gas Chromatography. 1979. 154 p. Protection Agency. Research Triangle Park,
ASTM D 2820–72, Part 23. Philadelphia, Pa. 14. Harris, W.E., H.W. Habgood. N.C. Publication No. EPA 600/2–76–201. July
23:950–958. 1973. Programmed Temperature Gas 1976. 71 p.
2. Corazon, V.V. Methodology for Chromatography. John Wiley and Sons, Inc. 22. Tentative Method for Continuous
Collecting and Analyzing Organic Air New York. 1966. Analysis of Total Hydrocarbons in the
Pollutants. U.S. Environmental Protection 15. Intersociety Committee. Methods of Air Atmosphere. Intersociety Committee,
Agency. Research Triangle Park, N.C. Sampling and Analysis. American Health American Public Health Association.
Publication No. EPA–600/2–79–042. Association. Washington, D.C. 1972. Washington, D.C. 1972. p. 184–186.
February 1979. 16. Jones, P.W., R.D. Grammer, P.E. Strup, 23. Zwerg, G. CRC Handbook of
3. Dravnieks, A., B.K. Krotoszynski, J. and T.B. Stanford. Environmental Science Chromatography, Volumes I and II. Sherma,
Whitfield, A. O’Donnell, and T. Burgwald. and Technology. 10:806–810. 1976. Joseph (ed.). CRC Press. Cleveland. 1972.

18.0 Tables, Diagrams, Flowcharts, and Validation Data
I. Name of company lllllllllllllllllllllllllllllllllllllllllllllllllllllll
Date llllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
Address lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

Contracts llllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
Phone llllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
Process to be sampled llllllllllllllllllllllllllllllllllllllllllllllllllllll
lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

Duct or vent to be sampled llllllllllllllllllllllllllllllllllllllllllllllllllll

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

II. Process description llllllllllllllllllllllllllllllllllllllllllllllllllllll

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

Raw material llllllllllllllllllllllllllllllllllllllllllllllllllllllllll

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

Products llllllllllllllllllllllllllllllllllllllllllllllllllllllllllll

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

Operating cycle
Check: Batch llll Continuous llll Cyclic llll
Timing of batch or cycle lllllllllllllllllllllllllllllllllllllllllllllllllllll

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Best time to test lllllllllllllllllllllllllllllllllllllllllllllllllllllllll
III. Sampling site lllllllllllllllllllllllllllllllllllllllllllllllllllllllll
A. Description llllllllllllllllllllllllllllllllllllllllllllllllllllllllll
Site decription llllllllllllllllllllllllllllllllllllllllllllllllllllllllll
Duct shape and size lllllllllllllllllllllllllllllllllllllllllllllllllllllll
Material lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
Wall thickness llll inches
Upstream distance llll inches llll diameter
Downstream distance llll inches llll diameter
Size of port lllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
Size of access area llllllllllllllllllllllllllllllllllllllllllllllllllllllll
Hazards llll Ambient temp. llll °F
B. Properties of gas stream
Temperature llll °C llll °F, Data source llll
Velocity llll, Data source llll
Static pressure llll inches H2O, Data source llll
Moisture content llll%, Data source llll
Particulate content llll, Data sourcellll
Gaseous components
N2 llll % Hydrocarbons llll ppm
O2 llll% llll
CO llll % llll llll
CO2 llll % llll llll
SO2 llll % llll llll
Hydrocarbon components
llll llll ppm

llll llll ppm

llll llll ppm

llll llll ppm

llll llll ppm

llll llll ppm

C. Sampling considerations
Location to set up GC lllllllllllllllllllllllllllllllllllllllllllllllllllllll

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

Special hazards to be considered lllllllllllllllllllllllllllllllllllllllllllllllll

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

Power available at duct llllllllllllllllllllllllllllllllllllllllllllllllllllll
Power available for GC llllllllllllllllllllllllllllllllllllllllllllllllllllll
Plant safety requirements lllllllllllllllllllllllllllllllllllllllllllllllllllll
lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

Vehicle traffic rules lllllllllllllllllllllllllllllllllllllllllllllllllllllll

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

Plant entry requirements lllllllllllllllllllllllllllllllllllllllllllllllllllll

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

Security agreements lllllllllllllllllllllllllllllllllllllllllllllllllllllll

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

Potential problems llllllllllllllllllllllllllllllllllllllllllllllllllllllll

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

D. Site diagrams. (Attach additional sheets if required).
Figure 18–1. Preliminary Survey Data Sheet
Components to be analyzed and Expected concentration
lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

Suggested chromatographic column llllllllllllllllllllllllllllllllllllllllllllllll

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

Column flow rate l ml/min
Head pressure llll mm Hg
Column temperature: Isothermal llll °C, Programmed from llll °C to llll °C at llll °C/min
Injection port/sample loop temperature llll °C
Detector temperature llll °C
Detector flow rates: Hydrogen llll ml/min., head pressure llll mm Hg, Air/Oxygen llll ml/min., head
pressure llll mm Hg.
Chart speed llll inches/minute

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Compound data:
Compound and Retention time and Attenuation
lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
l

Figure 18–2. Chromatographic Conditions Data Sheet

FIGURE 18–3. PREPARATION OF STANDARDS IN TEDLAR BAGS AND CALIBRATION CURVE
Standards

Mixture #1 Mixture #2 Mixture #3

Standards Preparation Data:
Organic:
Bag number or identification .............................................................................
Dry gas meter calibration factor ........................................................................
Final meter reading (liters) ................................................................................
Initial meter reading (liters) ...............................................................................
Metered volume (liters) .....................................................................................
Average meter temperature (°K) .......................................................................
Average meter pressure, gauge (mm Hg) ........................................................
Average atmospheric perssure (mm Hg) ..........................................................
Average meter pressure, absolute (mm Hg) ....................................................
Syringe temperature (°K) (see Section 10.1.2.1) ..............................................
Syringe pressure, absolute (mm Hg) (see Section 10.1.2.1) ...........................
Volume of gas in syringe (ml) (Section 10.1.2.1) .............................................
Density of liquid organic (g/ml) (Section 10.1.2.1) ............................................
Volume of liquid in syringe (ml) (Section 10.1.2.1) ...........................................
GC Operating Conditions:
Sample loop volume (ml) .........................................................................................
Sample loop temperature (°C) .................................................................................
Carrier gas flow rate (ml/min) ...................................................................................
Column temperature:
Initial (°C) ..................................................................................................................
Rate change (°C/min) ...............................................................................................
Final (°C) ..................................................................................................................
Organic Peak Identification and Calculated Concentrations:
Injection time (24 hour clock) ...................................................................................
Distance to peak (cm) ..............................................................................................
Chart speed (cm/min) ...............................................................................................
Organic retention time (min) .....................................................................................
Attenuation factor .....................................................................................................
Peak height (mm) .....................................................................................................
Peak area (mm2) ......................................................................................................
Peak area * attenuation factor (mm2) ......................................................................
Calculated concentration (ppm) (Equation 18–3 or 18–4) .......................................
Plot peak area * attenuation factor against calculated concentration to obtain calibration curve.
Flowmeter number or identification llllllllllllllllllllllllllllllllllllllllllllllll
Flowmeter Type lllllllllllllllllllllllllllllllllllllllllllllllllllllllll
Method: Bubble meterll Spirometerll Wet test meter ll

Readings at laboratory conditions:
Laboratory temperature (Tlab) ll °K
Laboratory barometric pressure (Plab)ll mm Hg
Flow data:

FLOWMETER
Reading (as marked) Temp. (°K) Pressure (absolute)

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CALIBRATION DEVICE
Time (min) Gas volume a Flow rate b

a Vol. of gas may be measured in milliliters, liters or cubic feet.
b Convert to standard conditions (20 °C and 760 mm Hg). Plot flowmeter reading against flow rate (standard conditions), and draw a smooth
curve. If the flowmeter being calibrated is a rotameter or other flow device that is viscosity dependent, it may be necessary to generate a ‘‘family’’
of calibration curves that cover the operating pressure and temperature ranges of the flowmeter. While the following technique should be verified
before application, it may be possible to calculate flow rate reading for rotameters at standard conditions Qstd as follows:

12
 760 × Tlab 
Q std = Q lab  
 Plab × 293 

Flow rate (laboratory conditions) Flow rate (STD conditions)

Figure 18–4. Flowmeter Calibration

BILLING CODE 6560–50–P

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BILLING CODE 6560–50–C

PREPARATION OF STANDARDS BY DILUTION OF CYLINDER STANDARD
[Cylinder Standard: Organic ———— Certified Concentration ———— ppm]

Date:
Standards preparation data:
Mixture 1 Mixture 2 Mixture 3

Stage 1:
Standard gas flowmeter reading.
Diluent gas flowmeter reading
Laboratory temperature (°K)
Barometric pressure (mm Hg)
Flowmeter gage pressure (mm Hg)
Flow rate cylinder gas at standard conditions (ml/min)
Flow rate diluent gas at standard conditions (ml/min)
Calculated concentration (ppm)
Stage 2 (if used):
Standard gas flowmeter reading
Diluent gas flowmeter reading
Flow rate Stage 1 gas at standard conditions (ml/min)
Flow rate diluent gas at standard conditions

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PREPARATION OF STANDARDS BY DILUTION OF CYLINDER STANDARD—Continued
[Cylinder Standard: Organic ———— Certified Concentration ———— ppm]

Date:
Standards preparation data:
Mixture 1 Mixture 2 Mixture 3

Calculated concentration (ppm)
GC Operating Conditions:
Sample loop volume (ml)
Sample loop temperature (°C)
Carrier gas flow rate (ml/min)
Column temperature:
Initial (°C)
Program rate (°C/min)
Final (°C)
Organic Peak Identification and Calculated Concentrations:
Injection time (24-hour clock)
Distance to peak (cm)
Chart speed (cm/min)
Retention time (min)
Attenuation factor
Peak area (mm 2)
Peak area *attenuation factor
Plot peak area *attenuation factor against calculated concentration to obtain calibration curve.

Figure 18–7. Standards Prepared by Dilution of Cylinder Standard

BILLING CODE 6560–50–P

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62024 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

BILLING CODE 6560–50–C

PLANTllll DATEllll SITEllll
Sample 1 Sample 2 Sample 3

Source temperature (°C) ............................................................................................................. ........................ ........................ ........................
Barometric pressure (mm Hg) ..................................................................................................... ........................ ........................ ........................
Ambient temperature (°C) ............................................................................................................ ........................ ........................ ........................
Sample flow rate (appr.) .............................................................................................................. ........................ ........................ ........................
Bag number ................................................................................................................................. ........................ ........................ ........................
Start time ..................................................................................................................................... ........................ ........................ ........................
Finish time ................................................................................................................................... ........................ ........................ ........................

Figure 18–10. Field Sample Data Sheet—Tedlar Bag Collection Method

PLANTllll DATEllll LOCATIONllll
1. General information:
Source temperature (°C) .......................................................................................................................................................... ............................
Probe temperature (°C) ............................................................................................................................................................ ............................
Ambient temperature (°C) ....................................................................................................................................................... ............................
Atmospheric pressure (mm) ................................................................................................................................................... ............................

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PLANT ———— DATE ———— LOCATION —————Continued
Source pressure (″Hg) .............................................................................................................................................................. ............................
Absolute source pressure (mm) .............................................................................................................................................. ............................
Sampling rate (liter/min) ........................................................................................................................................................ ............................
Sample loop volume (ml) ....................................................................................................................................................... ............................
Sample loop temperature (°C) ................................................................................................................................................ ............................
Columnar temperature:
Initial (°C) time (min) ...................................................................................................................................................... ............................
Program rate (°C/min) ...................................................................................................................................................... ............................
Final (°C)/time (min) ........................................................................................................................................................ ............................
Carrier gas flow rate (ml/min) ................................................................................................................................................ ............................
Detector temperature (°C) ....................................................................................................................................................... ............................
Injection time (24-hour basis) ................................................................................................................................................. ............................
Chart Speed (mm/min) ........................................................................................................................................................... ............................
Dilution gas flow rate (ml/min) .............................................................................................................................................. ............................
Dilution gas used (symbol) ..................................................................................................................................................... ............................
Dilution ratio ........................................................................................................................................................................... ............................

2. FIELD ANALYSIS DATA—CALIBRATION GAS
2. [Run No.llll Timellll]

Components Area Attenuation A x A Factor Conc.l (ppm)

Figure 18–11. Field Analysis Data Sheets

BILLING CODE 6560-50-P

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BILLING CODE 6560-50-C

GASEOUS ORGANIC SAMPLING AND ANALYSIS CHECK LIST
[Respond with initials or number as appropriate]

1. Presurvey data:
A. Grab sample collected ................................................................................................................................... b lll

B. Grab sample analyzed for composition ................................................................................................. b lll

Method GC ................................................................................................................................................... b lll

GC/MS ................................................................................................................................................... b lll

Other ..................................................................................................................................................... b lll

C. GC–FID analysis performed ........................................................................................................................... b lll

2. Laboratory calibration data:
A. Calibration curves prepared .......................................................................................................................... b lll

Number of components ............................................................................................................................... b lll

Number of concentrations/component (3 required) .................................................................................. b lll

B. Audit samples (optional):
Analysis completed ............................................................................................................................................ b lll

Verified for concentration .................................................................................................................................. b lll

OK obtained for field work ................................................................................................................................ b lll

3. Sampling procedures:
A. Method:
Bag sample ................................................................................................................................................... b lll

Direct interface ............................................................................................................................................ b lll

Dilution interface ......................................................................................................................................... b lll

B. Number of samples collected ........................................................................................................................ b lll

4. Field Analysis:
A. Total hydrocarbon analysis performed ........................................................................................................ b lll

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62028 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

GASEOUS ORGANIC SAMPLING AND ANALYSIS CHECK LIST—Continued
[Respond with initials or number as appropriate]
B. Calibration curve prepared ............................................................................................................................ b lll

Number of components ............................................................................................................................... b lll

Number of concentrations per component (3 required) ........................................................................... b lll

Gaseous Organic Sampling and Analysis Data
Plant llllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
Date llllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
Location llllllllllllllllllllllllllllllllllllllllllllllllllllllllllll

Source sample 1 Source sample 2 Source sample 3

1. General information:
Source temperature (°C) ......................................................................................................
Probe temperature (°C) ........................................................................................................
Ambient temperature (°C) .....................................................................................................
Atmospheric pressure (mm Hg) ............................................................................................
Source pressure (mm Hg) ....................................................................................................
Sampling rate (ml/min) ..........................................................................................................
Sample loop volume (ml) ......................................................................................................
Sample loop temperature (°C) ..............................................................................................
Sample collection time (24-hr basis) ....................................................................................
Column temperature:
Initial (°C) .......................................................................................................................
Program rate (°C/min) ...................................................................................................
Final (°C) .......................................................................................................................
Carrier gas flow rate (ml/min) ...............................................................................................
Detector temperature (°C) ....................................................................................................
Chart speed (cm/min) ...........................................................................................................
Dilution gas flow rate (ml/min) ..............................................................................................
Diluent gas used (symbol) ....................................................................................................
Dilution ratio ..........................................................................................................................
Performed by: (signature):llllllllllll Date:llllllllllll

Figure 18–14. Sampling and Analysis Sheet
Method 19—Determination of Sulfur Dioxide Removal Efficiency and Particulate Matter, Sulfur Dioxide, and Nitrogen
Oxide Emission Rates
1.0 Scope and Application
1.1 Analytes. This method provides data reduction procedures relating to the following pollutants, but does not
include any sample collection or analysis procedures.

Analyte CAS No. Sensitivity

Nitrogen oxides (NOX), includ-
ing:
Nitric oxide (NO) ................ 10102–43–9 ..................................................... N/A
Nitrogen dioxide (NO2) ...... 10102–44–0.
Particulate matter (PM) ............. None assigned ................................................. N/A
Sulfur dioxide (SO2) .................. 7499–09–05 ..................................................... N/A

1.2 Applicability. Where specified combustion gas volumes to heat inputs) analysis of the sulfur and heat contents
by an applicable subpart of the are used to calculate pollutant emission of the fuel before and after the
regulations, this method is applicable rates from pollutant concentrations. pretreatment system.
for the determination of (a) PM, SO2, 2.2 Sulfur Reduction Efficiency and 2.2.2 The SO2 removal efficiency of
and NOX emission rates; (b) sulfur SO2 Removal Efficiency. An overall SO2 a control device is determined by
removal efficiencies of fuel pretreatment emission reduction efficiency is measuring the SO2 rates before and after
and SO2 control devices; and (c) overall computed from the efficiency of fuel the control device.
reduction of potential SO2 emissions. pretreatment systems, where applicable,
and the efficiency of SO2 control 2.2.2.1 The inlet rates to SO2 control
2.0 Summary of Method systems (or, when SO2 control systems
devices.
are not used, SO2 emission rates to the
2.1 Emission Rates. Oxygen (O2) or 2.2.1 The sulfur removal efficiency
atmosphere) are determined by fuel
carbon dioxide (CO2) concentrations of a fuel pretreatment system is
and appropriate F factors (ratios of determined by fuel sampling and sampling and analysis.

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3.0 Definitions [Reserved] inlet, respectively, ng/J (lb/million nt = Total number of hourly averages for
4.0 Interferences [Reserved] Btu) or ppm corrected to 7 percent which paired inlet and outlet
O2. pollutant rates are available within
5.0 Safety [Reserved] Eh = Hourly average pollutant, ng/J (lb/ the 24-hr midnight to midnight
6.0 Equipment and Supplies million Btu). daily period.
[Reserved] Ehj = Hourly arithmetic average %O = Concentration of oxygen from an
pollutant rate for hour ‘‘j,’’ ng/J (lb/ ultimate analysis of fuel, weight
7.0 Reagents and Standards [Reserved] million Btu) or ppm corrected to 7 percent.
8.0 Sample Collection, Preservation, percent O2. %O2d, %O2w = Concentration of oxygen
Storage, and Transport [Reserved] EXP = Natural logarithmic base (2.718) on a dry and wet basis, respectively,
raised to the value enclosed by percent.
9.0 Quality Control [Reserved]
brackets. Ps = Potential SO2 emissions, percent.
10.0 Calibration and Standardization Fd, Fw, Fc = Volumes of combustion %Rf = SO2 removal efficiency from fuel
[Reserved] components per unit of heat pretreatment, percent.
11.0 Analytical Procedures [Reserved] content, scm/J (scf/million Btu).
%Rg = SO2 removal efficiency of the
GCV = Gross calorific value of the fuel
12.0 Data Analysis and Calculations control device, percent.
consistent with the ultimate
analysis, kJ/kg (Btu/lb). %Rga = Daily geometric average percent
12.1 Nomenclature reduction.
Bwa = Moisture fraction of ambient air, GCVp, GCVr = Gross calorific value for
the product and raw fuel lots, %Ro = Overall SO2 reduction, percent.
percent. %S = Sulfur content of as-fired fuel lot,
Bws = Moisture fraction of effluent gas, respectively, dry basis, kJ/kg (Btu/
lb). dry basis, weight percent.
percent.
%C = Concentration of carbon from an %H = Concentration of hydrogen from Se = Standard deviation of the hourly
ultimate analysis of fuel, weight an ultimate analysis of fuel, weight average pollutant rates for each
percent. percent. performance test period, ng/J (lb/
Cd = Pollutant concentration, dry basis, H = Total number of operating hours for million Btu).
ng/scm (lb/scf) which pollutant rates are %Sf = Concentration of sulfur from an
%CO2d,%CO2w = Concentration of determined in the performance test ultimate analysis of fuel, weight
carbon dioxide on a dry and wet period. percent.
basis, respectively, percent. Hb = Heat input rate to the steam Si = Standard deviation of the hourly
Cw = Pollutant concentration, wet basis, generating unit from fuels fired in average inlet pollutant rates for
ng/scm (lb/scf). the steam generating unit, J/hr each performance test period, ng/J
D = Number of sampling periods during (million Btu/hr). (lb/million Btu).
the performance test period. Hg = Heat input rate to gas turbine from So = Standard deviation of the hourly
E = Pollutant emission rate, ng/J (lb/ all fuels fired in the gas turbine, J/ average emission rates for each
million Btu). hr (million Btu/hr). performance test period, ng/J (lb/
Ea = Average pollutant rate for the %H2O = Concentration of water from an million Btu).
specified performance test period, ultimate analysis of fuel, weight %Sp, %Sr = Sulfur content of the
ng/J (lb/million Btu). percent. product and raw fuel lots
Eao, Eai = Average pollutant rate of the Hr = Total numbers of hours in the respectively, dry basis, weight
control device, outlet and inlet, performance test period (e.g., 720 percent.
respectively, for the performance hours for 30-day performance test t0.95 = Values shown in Table 19–3 for
test period, ng/J (lb/million Btu). period). the indicated number of data points
Ebi = Pollutant rate from the steam K = Conversion factor, 10¥5 (kJ/J)/(%) n.
generating unit, ng/J (lb/million [106 Btu/million Btu]. Xk = Fraction of total heat input from
Btu) Kc = (9.57 scm/kg)/% [(1.53 scf/lb)/%]. each type of fuel k.
Ebo = Pollutant emission rate from the Kcc = (2.0 scm/kg)/% [(0.321 scf/lb)/%].
steam generating unit, ng/J (lb/ Khd = (22.7 scm/kg)/% [(3.64 scf/lb)/%]. 12.2 Emission Rates of PM, SO2, and
million Btu). Khw = (34.74 scm/kg)/% [(5.57 scf/lb)/ NOx. Select from the following sections
Eci = Pollutant rate in combined %]. the applicable procedure to compute the
effluent, ng/J (lb/million Btu). Kn = (0.86 scm/kg)/% [(0.14 scf/lb)/%]. PM, SO2, or NOx emission rate (E) in ng/
Eco = Pollutant emission rate in Ko = (2.85 scm/kg)/% [(0.46 scf/lb)/%]. J (lb/million Btu). The pollutant
combined effluent, ng/J (lb/million Ks = (3.54 scm/kg)/% [(0.57 scf/lb)/%]. concentration must be in ng/scm (lb/scf)
Btu). Kw = (1.30 scm/kg)/% [(0.21 scf/lb)/%]. and the F factor must be in scm/J (scf/
Ed = Average pollutant rate for each ln = Natural log of indicated value. million Btu). If the pollutant
sampling period (e.g., 24-hr Method Lp,Lr = Weight of the product and raw concentration (C) is not in the
6B sample or 24-hr fuel sample) or fuel lots, respectively, metric ton appropriate units, use Table 19–1 in
for each fuel lot (e.g., amount of fuel (ton). Section 17.0 to make the proper
bunkered), ng/J (lb/million Btu). %N = Concentration of nitrogen from an conversion. An F factor is the ratio of
Edi = Average inlet SO2 rate for each ultimate analysis of fuel, weight the gas volume of the products of
sampling period d, ng/J (lb/million percent. combustion to the heat content of the
Btu) N = Number of fuel lots during the fuel. The dry F factor (Fd) includes all
Eg = Pollutant rate from gas turbine, ng/ averaging period. components of combustion less water,
J (lb/million Btu). n = Number of fuels being burned in the wet F factor (Fw) includes all
Ega = Daily geometric average pollutant combination. components of combustion, and the
rate, ng/J (lbs/million Btu) or ppm nd = Number of operating hours of the carbon F factor (Fc) includes only
corrected to 7 percent O2. affected facility within the carbon dioxide.
Ejo,Eji = Matched pair hourly arithmetic performance test period for each Ed Note: Since Fw factors include water
average pollutant rate, outlet and determined. resulting only from the combustion of

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hydrogen in the fuel, the procedures using Fw 12.2.1 Oxygen-Based F Factor, Dry 20.9
E = C d Fd Eq. 19-1
factors are not applicable for computing E
from steam generating units with wet
Basis. When measurements are on a dry
basis for both O (%O2d) and pollutant (20.9 − %O2 d )
scrubbers or with other processes that add (Cd) concentrations, use the following
water (e.g., steam injection). equation:

12.2.2 Oxygen-Based F Factor, Wet Basis. When measurements are on a wet basis for both O2 (%O2w) and pollutant
(Cw) concentrations, use either of the following:
12.2.2.1 If the moisture fraction of ambient air (Bwa) is measured:

20.9
E = C w Fw
[ ]
Eq. 19-2
20.9 (1 − Bwa ) − %O 2 w
Instead of actual measurement, Bwa may be estimated according to the procedure below.
NOTE: The estimates are selected to ensure that negative errors will not be larger than ¥1.5 percent. However,
positive errors, or over-estimation of emissions by as much as 5 percent may be introduced depending upon the geographic
location of the facility and the associated range of ambient moisture.
12.2.2.1.1 Bwa = 0.027. This value may be used at any location at all times.
12.2.2.1.2 Bwa = Highest monthly average of Bwa that occurred within the previous calendar year at the nearest
Weather Service Station. This value shall be determined annually and may be used as an estimate for the entire current
calendar year.
12.2.2.1.3 Bwa = Highest daily average of Bwa that occurred within a calendar month at the nearest Weather Service
Station, calculated from the data from the past 3 years. This value shall be computed for each month and may be
used as an estimate for the current respective calendar month.
12.2.2.2 If the moisture fraction (Bws) of the effluent gas is measured:

20.9
E = C w Fd
[ ]
Eq. 19-3
20.9 (1 − Bws ) − %O 2 w

12.2.3 Oxygen-Based F Factor, Dry/ 100 generating unit or the percent reduction
Wet Basis. E = C w Fc Eq. 19-7 in potential SO2 emissions as follows:
12.2.3.1 When the pollutant %CO 2 w
12.2.8.1 Compute the emission rate
concentration is measured on a wet 12.2.6 Carbon Dioxide-Based F
from the steam generating unit using the
basis (Cw) and O2 concentration is Factor, Dry/Wet Basis.
measured on a dry basis (%O2d), use the following equation:
12.2.6.1 When the pollutant
following equation: concentration is measured on a wet
(E )
Hg
basis (Cw) and CO2 concentration is E bo = E co + − Eg Eq. 19-10
(C w Fd )(20.9)
co
measured on a dry basis (%CO2d), use Hb
E= Eq. 19-4
(1 − Bws )(20.9 − %O2 d ) the following equation:
12.2.8.1.1 Use the test methods and
12.2.3.2 When the pollutant C w Fc 100 procedures section of 40 CFR Part 60,
E= Eq. 19-8
concentration is measured on a dry
basis (Cd) and the O2 concentration is
(1 − Bws ) %CO2 d Subpart GG to obtain Eco and Eg. Do not
use Fw factors for determining Eg or Eco.
measured on a wet basis (%O2w), use the 12.2.6.2 When the pollutant If an SO2 control device is used,
following equation: concentration is measured on a dry measure Eco after the control device.
basis (Cd) and CO2 concentration is 12.2.8.1.2 Suitable methods shall be
C d Fd 20.9 measured on a wet basis (%CO2w), use
E= Eq. 19-5 used to determine the heat input rates
(20.9 − %O2 w ) the following equation: to the steam generating units (Hb) and
(1 − Bws ) E = C d Fc (1 − Bws )
100
Eq. 19-9
the gas turbine (Hg).
12.2.4 Carbon Dioxide-Based F 12.2.8.2 If a control device is used,
%CO 2 w compute the percent of potential SO2
Factor, Dry Basis. When measurements
are on a dry basis for both CO2 (%CO2d) 12.2.7 Direct-Fired Reheat Fuel emissions (Ps) using the following
and pollutant (Cd) concentrations, use Burning. The effect of direct-fired reheat equations:
the following equation: fuel burning (for the purpose of raising

(E )
the temperature of the exhaust effluent Hg
from wet scrubbers to above the E bi = E ci − ci − Eg Eq. 19-11
100 Hb
E = C d Fc Eq. 19-6 moisture dew-point) on emission rates
%CO 2 d will be less than 1.0 percent and,
12.2.5 Carbon Dioxide-Based F therefore, may be ignored.
Factor, Wet Basis. When measurements 12.2.8 Combined Cycle-Gas Turbine  E 
are on a wet basis for both CO2 (%CO2w) Systems. For gas turbine-steam Ps = 100 1 − bo  Eq. 19-12
and pollutant (Cw) concentrations, use generator combined cycle systems,  E bi 
the following equation: determine the emissions from the steam

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NOTE: Use the test methods and procedures section of Subpart GG to obtain Eci and Eg. Do not use Fw factors
for determining Eg or Eci.
12.3 F Factors. Use an average F factor according to Section 12.3.1 or determine an applicable F factor according
to Section 12.3.2. If combined fuels are fired, prorate the applicable F factors using the procedure in Section 12.3.3.
12.3.1 Average F Factors. Average F factors (Fd, Fw, or Fc) from Table 19–2 in Section 17.0 may be used.
12.3.2 Determined F Factors. If the fuel burned is not listed in Table 19–2 or if the owner or operator chooses
to determine an F factor rather than use the values in Table 19–2, use the procedure below:
12.3.2.1 Equations. Use the equations below, as appropriate, to compute the F factors:

K (K hd %H + K c %C + K s %S + K n %N − K o %O)
Fd = Eq. 19-13
GCV

K[K hw %H + K c %C + K s %S + K n %N − K o %O + K w %H 2 O]
Fw = Eq. 19-14
GCVw

K (K cc %C) n determined from combinations of 1-
Fc = Eq. 19-15 Fw = ∑ ( X k Fwk ) Eq. 19-17 hour and longer than 1-hour periods
GCV k =1 (e.g., CEMS and Method 6B values),
Note: Omit the %H2O term in the compute the average pollutant rate (Ea)
equations for Fw if %H and %O include the for the performance test period (e.g., 30
unavailable hydrogen and oxygen in the form n days) specified in the applicable
of H2O.) Fc = ∑ ( X k Fck ) Eq. 19-18 regulation using the following equation:
12.3.2.2 Use applicable sampling k =1
D
∑ (n d E d ) j
procedures in Section 12.5.2.1 or 12.4 Determination of Average
12.5.2.2 to obtain samples for analyses. Pollutant Rates.
j=1
12.3.2.3 Use ASTM D 3176–74 or 89 12.4.1 Average Pollutant Rates from Ea = D Eq. 19-20
(all cited ASTM standards are
incorporated by reference—see § 60.17)
Hourly Values. When hourly average
pollutant rates (Eh), inlet or outlet, are ∑ n dj
j=1
for ultimate analysis of the fuel. obtained (e.g., CEMS values), compute
12.3.2.4 Use applicable methods in the average pollutant rate (Ea) for the 12.4.3 Daily Geometric Average
Section 12.5.2.1 or 12.5.2.2 to determine performance test period (e.g., 30 days) Pollutant Rates from Hourly Values. The
the heat content of solid or liquid fuels. specified in the applicable regulation geometric average pollutant rate (Ega) is
For gaseous fuels, use ASTM D 1826–77 using the following equation: computed using the following equation:
or 94 (incorporated by reference—see
1 
∑ [1n(E hj )]
nt
1 n
∑ E hj
§ 60.17) to determine the heat content.
Ea = Eq. 19-19 E ga = exp  Eq. 19-21
12.3.3 F Factors for Combination of H j=1  n t 
j=1
Fuels. If combinations of fuels are
burned, use the following equations, as 12.4.2 Average Pollutant Rates from 12.5 Determination of Overall
applicable unless otherwise specified in Other than Hourly Averages. When Reduction in Potential Sulfur Dioxide
an applicable subpart: pollutant rates are determined from Emission.
measured values representing longer 12.5.1 Overall Percent Reduction.
n than 1-hour periods (e.g., daily fuel Compute the overall percent SO2
Fd = ∑ ( X k Fdk ) Eq. 19-16 sampling and analyses or Method 6B reduction (%Ro) using the following
k =1 values), or when pollutant rates are equation:

 %R f   %R g  
%R o = 100 1.0 − 1.0 − 1.0 −  Eq. 19-22
  100   100  
12.5.2 Pretreatment Removal Efficiency (Optional). Compute the SO2 removal efficiency from fuel pretreatment (%Rf)
for the averaging period (e.g., 90 days) as specified in the applicable regulation using the following equation:

 N  %S
pj 



∑  GCV  L pj 

j=1  pj 
%R f = 100 1.0 −  Eq. 19-23
N  %S 

 ∑  GCV  rj 
rj
L
 j=1 rj 

Note: In calculating %Rf, include %S and pretreated and are used during the averaging 12.5.2.1 Solid Fossil (Including
GCV values for all fuel lots that are not period. Waste) Fuel/Sampling and Analysis.

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Note: For the purposes of this method, raw 12.5.2.1.3 Gross Sample Analysis. The owner or operator of an affected
fuel (coal or oil) is the fuel delivered to the Use ASTM D 2013–72 or 86 to prepare facility may elect to determine the GCV
desulfurization (pretreatment) facility. For the sample, ASTM D 3177–75 or 89 or by sampling the oil combusted on the
oil, the input oil to the oil desulfurization ASTM D 4239–85, 94, or 97 to first steam generating unit operating day
process (e.g., hydrotreatment) is considered
to be the raw fuel.
determine sulfur content (%S), ASTM D of each calendar month and then using
3173–73 or 87 to determine moisture the lowest GCV value of the three GCV
12.5.2.1.1 Sample Increment content, and ASTM D 2015–77 values per quarter for the GCV of all oil
Collection. Use ASTM D 2234–76, 96, (Reapproved 1978) or 96, D 3286–85 or combusted in that calendar quarter.
97a, or 98 (incorporated by reference— 96, or D 5865–98 to determine gross
see § 60.17), Type I, Conditions A, B, or 12.5.2.3 Use appropriate procedures,
calorific value (GCV) (all standards cited subject to the approval of the
C, and systematic spacing. As used in
are incorporated by reference—see Administrator, to determine the fraction
this method, systematic spacing is
§ 60.17 for acceptable versions of the of total mass input derived from each
intended to include evenly spaced
standards) on a dry basis for each gross type of fuel.
increments in time or increments based
sample.
on equal weights of coal passing the 12.5.3 Control Device Removal
12.5.2.2 Liquid Fossil Fuel-
collection area. As a minimum, Efficiency. Compute the percent
Sampling and Analysis. See Note under
determine the number and weight of removal efficiency (%Rg) of the control
Section 12.5.2.1.
increments required per gross sample device using the following equation:
12.5.2.2.1 Sample Collection. Follow
representing each coal lot according to
the procedures for continuous sampling
Table 2 or Paragraph 7.1.5.2 of ASTM D
in ASTM D 270 or D 4177–95  E 
2234. Collect one gross sample for each %R g = 100 1.0 − ao  Eq. 19-24
lot of raw coal and one gross sample for
(incorporated by reference—see § 60.17)  E ai 
each lot of product coal. for each gross sample from each fuel lot.
12.5.2.2.2 Lot Size. For the purpose 12.5.3.1 Use continuous emission
12.5.2.1.2 ASTM Lot Size. For the
of Section 12.5.2 (fuel pretreatment), the monitoring systems or test methods, as
purpose of Section 12.5.2 (fuel
lot size of a product oil is the weight of appropriate, to determine the outlet SO2
pretreatment), the lot size of product
product oil from one pretreatment rates and, if appropriate, the inlet SO2
coal is the weight of product coal from
one type of raw coal. The lot size of raw facility and intended as one shipment rates. The rates may be determined as
coal is the weight of raw coal used to (ship load, barge load, etc.). The lot size hourly (Eh) or other sampling period
produce one lot of product coal. of raw oil is the weight of each crude averages (Ed). Then, compute the
Typically, the lot size is the weight of liquid fuel type used to produce a lot of average pollutant rates for the
coal processed in a 1-day (24-hour) product oil. performance test period (Eao and Eai)
period. If more than one type of coal is Note: Alternative definitions of lot sizes using the procedures in Section 12.4.
treated and produced in 1 day, then may be used, subject to prior approval of the 12.5.3.2 As an alternative, as-fired
gross samples must be collected and Administrator. fuel sampling and analysis may be used
analyzed for each type of coal. A coal 12.5.2.2.3 Sample Analysis. Use to determine inlet SO2 rates as follows:
lot size equaling the 90-day quarterly ASTM D 129–64, 78, or 95, ASTM D 12.5.3.2.1 Compute the average inlet
fuel quantity for a steam generating unit 1552–83 or 95, or ASTM D 4057–81 or SO2 rate (Edi) for each sampling period
may be used if representative sampling 95 to determine the sulfur content (%S) using the following equation:
can be conducted for each raw coal and and ASTM D 240–76 or 92 (all
product coal. standards cited are incorporated by %S
Note: Alternative definitions of lot sizes reference—see § 60.17) to determine the E di = K Eq. 19-25
GCV of each gross sample. These values GCV
may be used, subject to prior approval of the
Administrator. may be assumed to be on a dry basis. Where:

ng SO 2   ( kJ )   1    1 
K = 2 × 10 7  2 × 10 4 
lb SO 2   Btu
       %S   million Btu   lb coal  
%S   J   kg coal  

After calculating Edi, use the procedures is the weight of oil supplied to the without oil being added to the oil ‘‘day’’
in Section 12.4 to determine the average ‘‘day’’ tank or consumed during each tank, the oil analysis from the previous
inlet SO2 rate for the performance test steam generating unit operating day. For day shall be used until the ‘‘day’’ tank
period (Eai). reporting and calculation purposes, the is filled again. Alternative definitions of
12.5.3.2.2 Collect the fuel samples gross sample shall be identified with the fuel lot size may be used, subject to
from a location in the fuel handling calendar day on which sampling began. prior approval of the Administrator.
system that provides a sample For steam generating unit operating 12.5.3.2.3 Use ASTM procedures
representative of the fuel bunkered or days when a coal-fired steam generating specified in Section 12.5.2.1 or 12.5.2.2
consumed during a steam generating unit is operated without coal being to determine %S and GCV.
unit operating day. For the purpose of added to the bunkers, the coal analysis
from the previous ‘‘as bunkered’’ coal 12.5.4 Daily Geometric Average
as-fired fuel sampling under Section
sample shall be used until coal is Percent Reduction from Hourly Values.
12.5.3.2 or Section 12.6, the lot size for
bunkered again. For steam generating The geometric average percent
coal is the weight of coal bunkered or
unit operating days when an oil-fired reduction (%Rga) is computed using the
consumed during each steam generating
steam generating unit is operated following equation:
unit operating day. The lot size for oil

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  1 nt E jo  
%R ga = 100 1 − EXP ∑ 1n  Eq. 19-26
  n t j=1 E ji  
NOTE: The calculation includes only paired data sets (hourly average) for the inlet and outlet pollutant measurements.
12.6 Sulfur Retention Credit for Compliance Fuel. If fuel sampling and analysis procedures in Section 12.5.2.1
are being used to determine average SO2 emission rates (Eas) to the atmosphere from a coal-fired steam generating
unit when there is no SO2 control device, the following equation may be used to adjust the emission rate for sulfur
retention credits (no credits are allowed for oil-fired systems) (Edi) for each sampling period using the following equation:

%S Where:
E di = 0.97K Eq. 19-27
GDV

ng SO 2   kJ   1     l 
K = 2 × 10 7  4  lb SO 2   Btu
  2 × 10 
 %S   J   kg coal   %S   million Btu   lb coal  

After calculating Edi, use the 12.7.1.1 Emission Rate. Compliance calculating the control device removal
procedures in Section 12.4.2 to with the emission rate standard may be efficiency (%Rg) as follows:
determine the average SO2 emission rate determined by using the lower
to the atmosphere for the performance confidence limit of the emission rate  E* 
test period (Eao). (Eao*) as follows: %R g = 100 1.0 − ao  Eq. 19-29
12.7 Determination of Compliance  E a*i 
When Minimum Data Requirement Is *
E ao = E ao − t 0.95 S o Eq. 19-28
Not Met.
12.7.1 Adjusted Emission Rates and 12.7.1.2 Control Device Removal
Control Device Removal Efficiency. Efficiency. Compliance with the overall E a*i = E a i + t 0.95 S i Eq. 19-30
When the minimum data requirement is emission reduction (%Ro) may be
not met, the Administrator may use the 12.7.2 Standard Deviation of Hourly
determined by using the lower Average Pollutant Rates. Compute the
following adjusted emission rates or confidence limit of the emission rate
control device removal efficiencies to standard deviation (Se) of the hourly
(Eao*) and the upper confidence limit of average pollutant rates using the
determine compliance with the
the inlet pollutant rate (Eai*) in following equation:
applicable standards.

∑ (E hj − E a )
H 2

1 1 j=1
Se = − Eq. 19-31
H Hr H −1
Equation 19–19 through 19–31 may be used to compute the standard deviation for both the outlet (So) and, if
applicable, inlet (Si) pollutant rates.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References [Reserved]

17.0 Tables, Diagrams, Flowcharts, and Validation Data

TABLE 19–1.—CONVERSION FACTORS FOR CONCENTRATION
From To Multiply by

g/scm ........................................................................................................................................................ ng/scm .............. 109
mg/scm ..................................................................................................................................................... ng/scm .............. 106
lb/scf .......................................................................................................................................................... ng/scm .............. 1.602 × 1013
ppm SO2 ................................................................................................................................................... ng/scm .............. 2.66 × 106
ppm NOx ................................................................................................................................................... ng/scm .............. 1.912 × 106
ppm SO2 ................................................................................................................................................... lb/scf ................. 1.660 × 10¥7
ppm NOx ................................................................................................................................................... lb/scf ................. 1.194 × 10¥7

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62034 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

TABLE 19–2.—F FACTORS FOR VARIOUS FUELS1
Fd Fw Fc
Fuel Type
dscm/J dscf/106 Btu wscm/J wscf/106 Btu scm/J scf/106 Btu

Coal:
Anthracite 2 ........................................ 2.71×10¥7 10,100 2.83×10¥7 10,540 0.530×10¥7 1,970
Bituminus 2 ........................................ 2.63×10¥7 9,780 2.86×10¥7 10,640 0.484×10¥7 1,800
Lignite ............................................... 2.65×10¥7 9,860 3.21×10¥7 11,950 0.513×10¥7 1,910
Oil 3 ................................................... 2.47×10¥7 9,190 2.77×10¥7 10,320 0.383×10¥7 1,420
Gas:.
Natural .............................................. 2.34×10¥7 8,710 2.85×10¥7 10,610 0.287×10¥7 1,040
Propane ............................................ 2.34×10¥7 8,710 2.74×10¥7 10,200 0.321×10¥7 1,190
Butane ............................................... 2.34×10¥7 8,710 2.79×10¥7 10,390 0.337×10¥7 1,250
Wood ........................................................ 2.48×10¥7 9,240 ........................ ........................ 0.492×10¥7 1,830
Wood Bark ............................................... 2.58×10¥7 9,600 ........................ ........................ 0.516×10¥7 1,920
Municipal .................................................. 2.57×10¥7 9,570 ........................ ........................ 0.488×10¥7 1,820
Solid Waste .............................................. ........................ ........................ ........................ ........................ ........................ ........................
1 Determined at standard conditions: 20 °C (68 °F) and 760 mm Hg (29.92 in Hg)
2 As classified according to ASTM D 388.
3 Crude, residual, or distillate.

TABLE 19–3.—VALUES FOR T0.95*
n1 t0.95 n1 t0.95 n1 t0.95

2 ..................................................................................................................... 6.31 8 1.89 22–26 1.71
3 ..................................................................................................................... 2.42 9 1.86 27–31 1.70
4 ..................................................................................................................... 2.35 10 1.83 32–51 1.68
5 ..................................................................................................................... 2.13 11 1.81 52–91 1.67
6 ..................................................................................................................... 2.02 12–16 1.77 92–151 1.66
7 ..................................................................................................................... 1.94 17–21 1.73 152 or more 1.65
1The values of this table are corrected for n-1 degrees of freedom. Use n equal to the number (H) of hourly average data points.

* * * * * contained in Section 6.0. A leak ambient concentration, that is less than
definition concentration based on a 2.5 percent of the specified leak
Method 21—Determination of Volatile
reference compound is specified in each definition concentration. that indicates
Organic Compound Leaks
applicable regulation. This method is that a VOC emission (leak) is not
1.0 Scope and Application intended to locate and classify leaks present.
1.1 Analytes. only, and is not to be used as a direct 3.5 Reference compound means the
measure of mass emission rate from
VOC species selected as the instrument
Analyte CAS No. individual sources.
calibration basis for specification of the
3.0 Definitions leak definition concentration. (For
Volatile Organic Com- No CAS number as-
pounds (VOC). signed. 3.1 Calibration gas means the VOC example, if a leak definition
compound used to adjust the instrument concentration is 10,000 ppm as
1.2 Scope. This method is applicable meter reading to a known value. The methane, then any source emission that
for the determination of VOC leaks from calibration gas is usually the reference results in a local concentration that
process equipment. These sources compound at a known concentration yields a meter reading of 10,000 on an
include, but are not limited to, valves, approximately equal to the leak instrument meter calibrated with
flanges and other connections, pumps definition concentration. methane would be classified as a leak.
and compressors, pressure relief 3.2 Calibration precision means the In this example, the leak definition
devices, process drains, open-ended degree of agreement between concentration is 10,000 ppm and the
valves, pump and compressor seal measurements of the same known value, reference compound is methane.)
system degassing vents, accumulator expressed as the relative percentage of 3.6 Response factor means the ratio
vessel vents, agitator seals, and access the average difference between the of the known concentration of a VOC
door seals. meter readings and the known compound to the observed meter
1.3 Data Quality Objectives. concentration to the known reading when measured using an
Adherence to the requirements of this concentration. instrument calibrated with the reference
method will enhance the quality of the 3.3 Leak definition concentration
compound specified in the applicable
data obtained from air pollutant means the local VOC concentration at
regulation.
sampling methods. the surface of a leak source that
indicates that a VOC emission (leak) is 3.7 Response time means the time
2.0 Summary of Method interval from a step change in VOC
present. The leak definition is an
2.1 A portable instrument is used to instrument meter reading based on a concentration at the input of the
detect VOC leaks from individual reference compound. sampling system to the time at which 90
sources. The instrument detector type is 3.4 No detectable emission means a percent of the corresponding final value
not specified, but it must meet the local VOC concentration at the surface is reached as displayed on the
specifications and performance criteria of a leak source, adjusted for local VOC instrument readout meter.

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4.0 Interferences. [Reserved] be encountered in its use. The the applicable regulation. Introduce the
5.0 Safety instrument shall, at a minimum, be calibration gas mixture to the analyzer
intrinsically safe for Class 1, Division 1 and record the observed meter reading.
5.1 Disclaimer. This method may conditions, and/or Class 2, Division 1 Introduce zero gas until a stable reading
involve hazardous materials, operations, conditions, as appropriate, as defined by is obtained. Make a total of three
and equipment. This test method may the example code. The instrument shall measurements by alternating between
not address all of the safety problems not be operated with any safety device, the calibration gas and zero gas.
associated with its use. It is the such as an exhaust flame arrestor, Calculate the response factor for each
responsibility of the user of this test removed. repetition and the average response
method to establish appropriate safety factor.
and health practices and determine the 7.0 Reagents and Standards 8.1.1.2 The instrument response
applicability of regulatory limitations 7.1 Two gas mixtures are required factors for each of the individual VOC
prior to performing this test method. for instrument calibration and to be measured shall be less than 10
5.2 Hazardous Pollutants. Several of performance evaluation: unless otherwise specified in the
the compounds, leaks of which may be 7.1.1 Zero Gas. Air, less than 10 applicable regulation. When no
determined by this method, may be parts per million by volume (ppmv) instrument is available that meets this
irritating or corrosive to tissues (e.g., VOC. specification when calibrated with the
heptane) or may be toxic (e.g., benzene, 7.1.2 Calibration Gas. For each reference VOC specified in the
methyl alcohol). Nearly all are fire organic species that is to be measured applicable regulation, the available
hazards. Compounds in emissions during individual source surveys, obtain instrument may be calibrated with one
should be determined through or prepare a known standard in air at a of the VOC to be measured, or any other
familiarity with the source. Appropriate concentration approximately equal to VOC, so long as the instrument then has
precautions can be found in reference the applicable leak definition specified a response factor of less than 10 for each
documents, such as reference No. 4 in in the regulation. of the individual VOC to be measured.
Section 16.0. 7.2 Cylinder Gases. If cylinder 8.1.1.3 Alternatively, if response
calibration gas mixtures are used, they factors have been published for the
6.0 Equipment and Supplies must be analyzed and certified by the compounds of interest for the
A VOC monitoring instrument manufacturer to be within 2 percent instrument or detector type, the
meeting the following specifications is accuracy, and a shelf life must be response factor determination is not
required: specified. Cylinder standards must be required, and existing results may be
6.1 The VOC instrument detector either reanalyzed or replaced at the end referenced. Examples of published
shall respond to the compounds being of the specified shelf life. response factors for flame ionization
processed. Detector types that may meet 7.3 Prepared Gases. Calibration and catalytic oxidation detectors are
this requirement include, but are not gases may be prepared by the user included in References 1–3 of Section
limited to, catalytic oxidation, flame according to any accepted gaseous 17.0.
ionization, infrared absorption, and preparation procedure that will yield a 8.1.2 Calibration Precision. The
photoionization. mixture accurate to within 2 percent. calibration precision test must be
6.2 The instrument shall be capable Prepared standards must be replaced completed prior to placing the analyzer
of measuring the leak definition each day of use unless it is into service and at subsequent 3-month
concentration specified in the demonstrated that degradation does not intervals or at the next use, whichever
regulation. occur during storage. is later.
6.3 The scale of the instrument 7.4 Mixtures with non-Reference 8.1.2.1 Make a total of three
meter shall be readable to ±2.5 percent Compound Gases. Calibrations may be measurements by alternately using zero
of the specified leak definition performed using a compound other than gas and the specified calibration gas.
concentration. the reference compound. In this case, a Record the meter readings. Calculate the
6.4 The instrument shall be conversion factor must be determined average algebraic difference between the
equipped with an electrically driven for the alternative compound such that meter readings and the known value.
pump to ensure that a sample is the resulting meter readings during Divide this average difference by the
provided to the detector at a constant source surveys can be converted to known calibration value and multiply
flow rate. The nominal sample flow rate, reference compound results. by 100 to express the resulting
as measured at the sample probe tip, calibration precision as a percentage.
shall be 0.10 to 3.0 l/min (0.004 to 0.1 8.0 Sample Collection, Preservation, 8.1.2.2 The calibration precision
ft3/min) when the probe is fitted with a Storage, and Transport shall be equal to or less than 10 percent
glass wool plug or filter that may be 8.1 Instrument Performance of the calibration gas value.
used to prevent plugging of the Evaluation. Assemble and start up the 8.1.3 Response Time. The response
instrument. instrument according to the time test is required before placing the
6.5 The instrument shall be manufacturer’s instructions for instrument into service. If a
equipped with a probe or probe recommended warmup period and modification to the sample pumping
extension or sampling not to exceed 6.4 preliminary adjustments. system or flow configuration is made
mm (1⁄4 in) in outside diameter, with a 8.1.1 Response Factor. A response that would change the response time, a
single end opening for admission of factor must be determined for each new test is required before further use.
sample. compound that is to be measured, either 8.1.3.1 Introduce zero gas into the
6.6 The instrument shall be by testing or from reference sources. The instrument sample probe. When the
intrinsically safe for operation in response factor tests are required before meter reading has stabilized, switch
explosive atmospheres as defined by the placing the analyzer into service, but do quickly to the specified calibration gas.
National Electrical Code by the National not have to be repeated at subsequent After switching, measure the time
Fire Prevention Association or other intervals. required to attain 90 percent of the final
applicable regulatory code for operation 8.1.1.1 Calibrate the instrument with stable reading. Perform this test
in any explosive atmospheres that may the reference compound as specified in sequence three times and record the

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62036 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

results. Calculate the average response complete traverse of the shaft periphery, 8.3.2.1 Pump or Compressor Seals. If
time. sample all accessible portions. Sample applicable, determine the type of shaft
8.1.3.2 The instrument response all other joints on the pump or seal. Perform a survey of the local area
time shall be equal to or less than 30 compressor housing where leakage ambient VOC concentration and
seconds. The instrument pump, dilution could occur. determine if detectable emissions exist
probe (if any), sample probe, and probe 8.3.1.4 Pressure Relief Devices. The as described in Section 8.3.2.
filter that will be used during testing configuration of most pressure relief 8.3.2.2 Seal System Degassing Vents,
shall all be in place during the response devices prevents sampling at the sealing Accumulator Vessel Vents, Pressure
time determination. seat interface. For those devices Relief Devices. If applicable, observe
8.2 Instrument Calibration. Calibrate equipped with an enclosed extension, or whether or not the applicable ducting or
the VOC monitoring instrument horn, place the probe inlet at piping exists. Also, determine if any
according to Section 10.0. approximately the center of the exhaust sources exist in the ducting or piping
8.3 Individual Source Surveys. area to the atmosphere. where emissions could occur upstream
8.3.1 Type I—Leak Definition Based 8.3.1.5 Process Drains. For open of the control device. If the required
on Concentration. Place the probe inlet drains, place the probe inlet at ducting or piping exists and there are no
at the surface of the component approximately the center of the area sources where the emissions could be
interface where leakage could occur. open to the atmosphere. For covered vented to the atmosphere upstream of
Move the probe along the interface drains, place the probe at the surface of the control device, then it is presumed
periphery while observing the the cover interface and conduct a that no detectable emissions are present.
instrument readout. If an increased peripheral traverse. If there are sources in the ducting or
meter reading is observed, slowly 8.3.1.6 Open-ended Lines or Valves. piping where emissions could be vented
sample the interface where leakage is Place the probe inlet at approximately or sources where leaks could occur, the
indicated until the maximum meter the center of the opening to the sampling surveys described in Section
reading is obtained. Leave the probe atmosphere. 8.3.2 shall be used to determine if
inlet at this maximum reading location 8.3.1.7 Seal System Degassing Vents detectable emissions exist.
for approximately two times the and Accumulator Vents. Place the probe 8.3.3 Alternative Screening
instrument response time. If the inlet at approximately the center of the Procedure.
maximum observed meter reading is opening to the atmosphere. 8.3.3.1 A screening procedure based
greater than the leak definition in the 8.3.1.8 Access door seals. Place the on the formation of bubbles in a soap
applicable regulation, record and report probe inlet at the surface of the door solution that is sprayed on a potential
the results as specified in the regulation seal interface and conduct a peripheral leak source may be used for those
reporting requirements. Examples of the traverse. sources that do not have continuously
application of this general technique to 8.3.2 Type II—‘‘No Detectable moving parts, that do not have surface
specific equipment types are: Emission’’. Determine the local ambient temperatures greater than the boiling
8.3.1.1 Valves. The most common VOC concentration around the source point or less than the freezing point of
source of leaks from valves is the seal by moving the probe randomly upwind the soap solution, that do not have open
between the stem and housing. Place the and downwind at a distance of one to areas to the atmosphere that the soap
probe at the interface where the stem two meters from the source. If an solution cannot bridge, or that do not
exits the packing gland and sample the interference exists with this exhibit evidence of liquid leakage.
stem circumference. Also, place the determination due to a nearby emission Sources that have these conditions
probe at the interface of the packing or leak, the local ambient concentration present must be surveyed using the
gland take-up flange seat and sample the may be determined at distances closer to instrument technique of Section 8.3.1 or
periphery. In addition, survey valve the source, but in no case shall the 8.3.2.
housings of multipart assembly at the distance be less than 25 centimeters.
8.3.3.2 Spray a soap solution over all
surface of all interfaces where a leak Then move the probe inlet to the surface
potential leak sources. The soap
could occur. of the source and determine the
solution may be a commercially
8.3.1.2 Flanges and Other concentration as outlined in Section
available leak detection solution or may
Connections. For welded flanges, place 8.3.1. The difference between these
be prepared using concentrated
the probe at the outer edge of the flange- concentrations determines whether
detergent and water. A pressure sprayer
gasket interface and sample the there are no detectable emissions.
or squeeze bottle may be used to
circumference of the flange. Sample Record and report the results as
dispense the solution. Observe the
other types of nonpermanent joints specified by the regulation. For those
potential leak sites to determine if any
(such as threaded connections) with a cases where the regulation requires a
bubbles are formed. If no bubbles are
similar traverse. specific device installation, or that
observed, the source is presumed to
8.3.1.3 Pumps and Compressors. specified vents be ducted or piped to a
have no detectable emissions or leaks as
Conduct a circumferential traverse at control device, the existence of these
applicable. If any bubbles are observed,
the outer surface of the pump or conditions shall be visually confirmed.
the instrument techniques of Section
compressor shaft and seal interface. If When the regulation also requires that
8.3.1 or 8.3.2 shall be used to determine
the source is a rotating shaft, position no detectable emissions exist, visual
if a leak exists, or if the source has
the probe inlet within 1 cm of the shaft- observations and sampling surveys are
detectable emissions, as applicable.
seal interface for the survey. If the required. Examples of this technique
housing configuration prevents a are: 9.0 Quality Control

Section Quality control measure Effect

8.1.2 .......................................... Instrument calibration precision check ............. Ensure precision and accuracy, respectively, of instrument re-
sponse to standard.
10.0 ........................................... Instrument calibration.

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10.0 Calibration and Standardization emissions from flares are visually 4.0 Interferences
10.1 Calibrate the VOC monitoring determined by an observer without the
4.1 Occasionally, fugitive emissions
instrument as follows. After the aid of instruments.
from sources other than the affected
appropriate warmup period and zero 2.2 This method is used also to facility (e.g., road dust) may prevent a
internal calibration procedure, determine visible smoke emissions from clear view of the affected facility. This
introduce the calibration gas into the flares used for combustion of waste may particularly be a problem during
instrument sample probe. Adjust the process materials. periods of high wind. If the view of the
instrument meter readout to correspond 2.3 This method determines the potential emission points is obscured to
to the calibration gas value. amount of time that visible emissions such a degree that the observer
Note: If the meter readout cannot be occur during the observation period questions the validity of continuing
adjusted to the proper value, a malfunction (i.e., the accumulated emission time). observations, then the observations shall
of the analyzer is indicated and corrective This method does not require that the be terminated, and the observer shall
actions are necessary before use. opacity of emissions be determined. clearly note this fact on the data form.
Since this procedure requires only the
11.0 Analytical Procedures. [Reserved] determination of whether visible 5.0 Safety
12.0 Data Analyses and Calculations. emissions occur and does not require 5.1 Disclaimer. This method may
[Reserved] the determination of opacity levels, involve hazardous materials, operations,
13.0 Method Performance. [Reserved] observer certification according to the and equipment. This test method may
procedures of Method 9 is not required. not address all of the safety problems
14.0 Pollution Prevention. [Reserved] However, it is necessary that the associated with its use. It is the
15.0 Waste Management. [Reserved] observer is knowledgeable with respect responsibility of the user of this test
to the general procedures for method to establish appropriate safety
16.0 References determining the presence of visible and health practices and determine the
1. Dubose, D.A., and G.E. Harris. Response emissions. At a minimum, the observer applicability of regulatory limitations
Factors of VOC Analyzers at a Meter Reading must be trained and knowledgeable
of 10,000 ppmv for Selected Organic prior to performing this test method.
regarding the effects of background
Compounds. U.S. Environmental Protection contrast, ambient lighting, observer 6.0 Equipment
Agency, Research Triangle Park, NC.
position relative to lighting, wind, and 6.1 Stopwatches (two).
Publication No. EPA 600/2–81051.
September 1981. the presence of uncombined water Accumulative type with unit divisions
2. Brown, G.E., et al. Response Factors of (condensing water vapor) on the of at least 0.5 seconds.
VOC Analyzers Calibrated with Methane for visibility of emissions. This training is
6.2 Light Meter. Light meter capable
Selected Organic Compounds. U.S. to be obtained from written materials
of measuring illuminance in the 50 to
Environmental Protection Agency, Research found in References 1 and 2 or from the
Triangle Park, NC. Publication No. EPA 600/ 200 lux range, required for indoor
lecture portion of the Method 9
2–81–022. May 1981. observations only.
certification course.
3. DuBose, D.A. et al. Response of Portable 7.0 Reagents and Supplies. [Reserved]
VOC Analyzers to Chemical Mixtures. U.S. 3.0 Definitions
Environmental Protection Agency, Research 8.0 Sample Collection, Preservation,
3.1 Emission frequency means the
Triangle Park, NC. Publication No. EPA 600/ Storage, and Transfer. [Reserved]
2–81–110. September 1981. percentage of time that emissions are
4. Handbook of Hazardous Materials: Fire, visible during the observation period. 9.0 Quality Control. [Reserved]
Safety, Health. Alliance of American 3.2 Emission time means the 10.0 Calibration and Standardization.
Insurers. Schaumberg, IL. 1983. accumulated amount of time that [Reserved]
emissions are visible during the
17.0 Tables, Diagrams, Flowcharts, 11.0 Analytical Procedure
observation period.
and Validation Data. [Reserved]
3.3 Fugitive emissions means 11.1 Selection of Observation
Method 22—Visual Determination of emissions generated by an affected Location. Survey the affected facility, or
Fugitive Emissions From Material facility which is not collected by a the building or structure housing the
Sources and Smoke Emissions From capture system and is released to the process to be observed, and determine
Flares atmosphere. This includes emissions the locations of potential emissions. If
that (1) escape capture by process the affected facility is located inside a
Note: This method is not inclusive with
respect to observer certification. Some
equipment exhaust hoods; (2) are building, determine an observation
material is incorporated by reference from emitted during material transfer; (3) are location that is consistent with the
Method 9. emitted from buildings housing material requirements of the applicable
processing or handling equipment; or regulation (i.e., outside observation of
1.0 Scope and Application (4) are emitted directly from process emissions escaping the building/
This method is applicable for the equipment. structure or inside observation of
determination of the frequency of 3.4 Observation period means the emissions directly emitted from the
fugitive emissions from stationary accumulated time period during which affected facility process unit). Then
sources, only as specified in an observations are conducted, not to be select a position that enables a clear
applicable subpart of the regulations. less than the period specified in the view of the potential emission point(s)
This method also is applicable for the applicable regulation. of the affected facility or of the building
determination of the frequency of 3.5 Smoke emissions means a or structure housing the affected facility,
visible smoke emissions from flares. pollutant generated by combustion in a as appropriate for the applicable
flare and occurring immediately subpart. A position at least 4.6 m (15
2.0 Summary of Method downstream of the flame. Smoke feet), but not more than 400 m (0.25
2.1 Fugitive emissions produced occurring within the flame, but not miles), from the emission source is
during material processing, handling, downstream of the flame, is not recommended. For outdoor locations,
and transfer operations or smoke considered a smoke emission. select a position where the sunlight is

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62038 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

not shining directly in the observer’s period. When the observation period is without taking a rest break. For sources
eyes. completed, record the clock time. requiring observation periods of greater
11.2 Field Records. During the observation period, than 20 minutes, the observer shall take
11.2.1 Outdoor Location. Record the continuously watch the emission a break of not less than 5 minutes and
following information on the field data source. Upon observing an emission not more than 10 minutes after every 15
sheet (Figure 22–1): Company name, (condensed water vapor is not to 20 minutes of observation. If
industry, process unit, observer’s name, considered an emission), start the continuous observations are desired for
observer’s affiliation, and date. Record second accumulative stopwatch; stop extended time periods, two observers
also the estimated wind speed, wind the watch when the emission stops. can alternate between making
direction, and sky condition. Sketch the Continue this procedure for the entire observations and taking breaks.
process unit being observed, and note observation period. The accumulated 11.5 Recording Observations. Record
the observer location relative to the elapsed time on this stopwatch is the the accumulated time of the observation
source and the sun. Indicate the total time emissions were visible during period on the data sheet as the
potential and actual emission points on the observation period (i.e., the observation period duration. Record the
the sketch. emission time.) accumulated time emissions were
11.2.2 Indoor Location. Record the 11.4.2 Observation Period. Choose observed on the data sheet as the
following information on the field data an observation period of sufficient emission time. Record the clock time
sheet (Figure 22–2): Company name, length to meet the requirements for the observation period began and ended,
industry, process unit, observer’s name, determining compliance with the as well as the clock time any observer
observer’s affiliation, and date. Record emission standard in the applicable breaks began and ended.
as appropriate the type, location, and subpart of the regulations. When the
12.0 Data Analysis and Calculations
intensity of lighting on the data sheet. length of the observation period is
Sketch the process unit being observed, specifically stated in the applicable If the applicable subpart requires that
and note the observer location relative subpart, it may not be necessary to the emission rate be expressed as an
to the source. Indicate the potential and observe the source for this entire period emission frequency (in percent),
actual fugitive emission points on the if the emission time required to indicate determine this value as follows: Divide
sketch. noncompliance (based on the specified the accumulated emission time (in
11.3 Indoor Lighting Requirements. observation period) is observed in a seconds) by the duration of the
For indoor locations, use a light meter shorter time period. In other words, if observation period (in seconds) or by
to measure the level of illumination at the regulation prohibits emissions for any minimum observation period
a location as close to the emission more than 6 minutes in any hour, then required in the applicable subpart, if the
source(s) as is feasible. An illumination observations may (optional) be stopped actual observation period is less than
of greater than 100 lux (10 foot candles) after an emission time of 6 minutes is the required period, and multiply this
is considered necessary for proper exceeded. Similarly, when the quotient by 100.
application of this method. regulation is expressed as an emission 13.0 Method Performance. [Reserved]
11.4 Observations. frequency and the regulation prohibits
11.4.1 Procedure. Record the clock emissions for greater than 10 percent of 14.0 Pollution Prevention. [Reserved]
time when observations begin. Use one the time in any hour, then observations 15.0 Waste Management. [Reserved]
stopwatch to monitor the duration of the may (optional) be terminated after 6
observation period. Start this stopwatch minutes of emission are observed since 16.0 References
when the observation period begins. If 6 minutes is 10 percent of an hour. In 1. Missan, R., and A. Stein. Guidelines for
the observation period is divided into any case, the observation period shall Evaluation of Visible Emissions Certification,
two or more segments by process not be less than 6 minutes in duration. Field Procedures, Legal Aspects, and
shutdowns or observer rest breaks (see In some cases, the process operation Background Material. EPA Publication No.
Section 11.4.3), stop the stopwatch may be intermittent or cyclic. In such EPA–340/1–75–007. April 1975.
2. Wohlschlegel, P., and D.E. Wagoner.
when a break begins and restart the cases, it may be convenient for the Guideline for Development of a Quality
stopwatch without resetting it when the observation period to coincide with the Assurance Program: Volume IX— Visual
break ends. Stop the stopwatch at the length of the process cycle. Determination of Opacity Emissions from
end of the observation period. The 11.4.3 Observer Rest Breaks. Do not Stationary Sources. EPA Publication No.
accumulated time indicated by this observe emissions continuously for a EPA–650/4–74–005i. November 1975.
stopwatch is the duration of observation period of more than 15 to 20 minutes BILLING CODE 6560–50–P

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17.0 Tables, Diagrams, Flowcharts, and Validation Data

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62040 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

BILLING CODE 6560–50–C

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Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations 62041

* * * * * corrosive to tissues (e.g., heptane) or replaced with appropriate confidence
may be toxic (e.g., benzene, methyl limits (Section 12.6). These confidence
Method 24—Determination of Volatile
alcohol). Nearly all are fire hazards. limits are based on measured
Matter Content, Water Content, Density,
Appropriate precautions can be found parameters and inter-laboratory
Volume Solids, and Weight Solids of
in reference documents, such as precision statements.
Surface Coatings
Reference 3 of Section 16.0.
10.0 Calibration and Standardization
1.0 Scope and Application
6.0 Equipment and Supplies
1.1 Analytes. 10.1 Perform the calibration and
The equipment and supplies specified standardization procedures specified in
Analyte CAS No. in the ASTM methods listed in Sections the ASTM methods listed in Sections
6.1 through 6.6 (incorporated by 6.1 through 6.6.
Volatile organic com- No CAS Number as- reference—see § 60.17 for acceptable
pounds Water. signed 7732–18–5 versions of the methods) are required: 11.0 Analytical Procedure
6.1 ASTM D 1475–60, 80, or 90, Additional guidance can be found in
1.2 Applicability. This method is Standard Test Method for Density of Reference 2 of Section 16.0.
applicable for the determination of Paint, Varnish, Lacquer, and Related 11.1 Non Thin-film Ultraviolet
volatile matter content, water content, Products. Radiation-cured (UV radiation-cured)
density, volume solids, and weight 6.2 ASTM D 2369–81, 87, 90, 92, 93, Coatings.
solids of paint, varnish, lacquer, or other or 95, Standard Test Method for Volatile 11.1.1 Volatile Content. Use the
related surface coatings. Content of Coatings. procedure in ASTM D 5403 to
1.3 Precision and Bias. Intra-and 6.3 ASTM D 3792–79 or 91, determine the volatile matter content of
inter-laboratory analytical precision Standard Test Method for Water Content the coating except the curing test
statements are presented in Section of Water Reducible Paints by Direct described in NOTE 2 of ASTM D 5403
13.1. No bias has been identified. Injection into a Gas Chromatograph. is required.
6.4 ASTM D 4017–81, 90, or 96a,
2.0 Summary of Method 11.1.2 Water Content. To determine
Standard Test Method for Water in
2.1 Standard methods are used to water content, follow Section 11.3.2.
Paints and Paint Materials by the Karl
determine the volatile matter content, Fischer Titration Method. 11.1.3 Coating Density. To
water content, density, volume solids, 6.5 ASTM 4457–85 91, Standard determine coating density, follow
and weight solids of paint, varnish, Test Method for Determination of Section 11.3.3.
lacquer, or other related surface Dichloromethane and 1,1,1- 11.1.4 Solids Content. To determine
coatings. Trichloroethane in Paints and Coatings solids content, follow Section 11.3.4.
by Direct Injection into a Gas 11.1.5 To determine if a coating or
3.0 Definitions ink can be classified as a thin-film UV
Chromatograph.
3.1 Waterborne coating means any 6.6 ASTM D 5403–93, Standard Test cured coating or ink, use the equation in
coating which contains more than 5 Methods for Volatile Content of Section 12.2. If C is less than 0.2 g and
percent water by weight in its volatile Radiation Curable Materials. A is greater than or equal to 225 cm2 (35
fraction. in2) then the coating or ink is
3.2 Multicomponent coatings are 7.0 Reagents and Standards considered a thin-film UV radiation-
coatings that are packaged in two or 7.1 The reagents and standards cured coating and ASTM D 5403 is not
more parts, which are combined before specified in the ASTM methods listed in applicable.
application. Upon combination a Sections 6.1 through 6.6 are required. Note: As noted in Section 1.4 of ASTM D
coreactant from one part of the coating 5403, this method may not be applicable to
8.0 Sample Collection, Preservation, radiation curable materials wherein the
chemically reacts, at ambient
Storage, and Transport volatile material is water.
conditions, with a coreactant from
another part of the coating. 8.1 Follow the sample collection, 11.2 Multi-component Coatings.
3.3 Ultraviolet (UV) radiation-cured preservation, storage, and transport 11.2.1 Sample Preparation.
coatings are coatings which contain procedures described in Reference 1 of 11.2.1.1 Prepare about 100 ml of
unreacted monomers that are Section 16.0. sample by mixing the components in a
polymerized by exposure to ultraviolet 9.0 Quality Control storage container, such as a glass jar
light. with a screw top or a metal can with a
9.1 Reproducibility cap. The storage container should be
4.0 Interferences. [Reserved] Note: Not applicable to UV radiation-cured just large enough to hold the mixture.
5.0 Safety coatings). The variety of coatings that may be
Combine the components (by weight or
subject to analysis makes it necessary to
5.1 Disclaimer. This method may verify the ability of the analyst and the volume) in the ratio recommended by
involve hazardous materials, operations, analytical procedures to obtain reproducible the manufacturer. Tightly close the
and equipment. This test method may results for the coatings tested. Verification is container between additions and during
not address all of the safety problems accomplished by running duplicate analyses mixing to prevent loss of volatile
associated with its use. It is the on each sample tested (Sections 11.2 through materials. However, most manufacturers
responsibility of the user of this test 11.4) and comparing the results with the mixing instructions are by volume.
method to establish appropriate safety intra-laboratory precision statements (Section Because of possible error caused by
and health practices and to determine 13.1) for each parameter. expansion of the liquid when measuring
the applicability of regulatory 9.2 Confidence Limits for the volume, it is recommended that the
limitations prior to performing this test Waterborne Coatings. Because of the components be combined by weight.
method. inherent increased imprecision in the When weight is used to combine the
5.2 Hazardous Components. Several determination of the VOC content of components and the manufacturer’s
of the compounds that may be waterborne coatings as the weight recommended ratio is by volume, the
contained in the coatings analyzed by percent of water increases, measured density must be determined by Section
this method may be irritating or parameters for waterborne coatings are 11.3.3.

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62042 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

11.2.1.2 Immediately after mixing, 11.3 Water-or Solvent-borne precision (excluding UV radiation-cured
take aliquots from this 100 ml sample coatings. coatings), the U.S. Environmental
for determination of the total volatile 11.3.1 Volatile Content. Use the Protection Agency (EPA) will assume
content, water content, and density. procedure in ASTM D 2369 to responsibility for providing the
11.2.2 Volatile Content. To determine the volatile matter content necessary procedures for revising the
determine total volatile content, use the (may include water) of the coating. method or precision statements upon
apparatus and reagents described in 11.3.1.1 Record the following written request to: Director, Emissions,
ASTM D2369 Sections 3 and 4 information: Monitoring, and Analysis Division, MD–
(incorporated by reference—see § 60.17 W1 = weight of dish and sample before 14, Office of Air Quality Planning and
for the approved versions of the heating, g Standards, U.S. Environmental
standard), respectively, and use the W2 = weight of dish and sample after Protection Agency, Research Triangle
following procedures: heating, g Park, NC 27711.
11.2.2.1 Weigh and record the W3 = sample weight, g.
weight of an aluminum foil weighing 12.0 Calculations and Data Analysis
11.3.1.2 Calculate the weight
dish. Add 3 ± 1 ml of suitable solvent 12.1 Nomenclature.
fraction of the volatile matter (Wv) for
as specified in ASTM D2369 to the A = Area of substrate, cm2, (in2).
each analysis as shown in Section 12.3.
weighing dish. Using a syringe as C = Amount of coating or ink added to
11.3.1.3 Run duplicate analyses
specified in ASTM D2369, weigh to 1 the substrate, g.
until the difference between the two
mg, by difference, a sample of coating Dc = Density of coating or ink, g/cm3 (g/
values in a set is less than or equal to
into the weighing dish. For coatings in3).
the intra-laboratory precision statement
believed to have a volatile content less F = Manufacturer’s recommended film
in Section 13.1.
than 40 weight percent, a suitable size thickness, cm (in).
11.3.1.4 Record the arithmetic
is 0.3 + 0.10 g, but for coatings believed Wo = Weight fraction of nonaqueous
average (Wv).
to have a volatile content greater than 40 11.3.2 Water Content. For volatile matter, g/g.
weight percent, a suitable size is 0.5 ± waterborne coatings only, determine the
Ws = Weight fraction of solids, g/g.
0.1 g. Wv = Weight fraction of the volatile
weight fraction of water (Ww) using
Note: If the volatile content determined matter, g/g.
either ASTM D 3792 or ASTM D 4017.
pursuant to Section 12.4 is not in the range Ww = Weight fraction of the water, g/g.
11.3.2.1 Run duplicate analyses 12.2 To determine if a coating or ink
corresponding to the sample size chosen
repeat the test with the appropriate sample until the difference between the two can be classified as a thin-film UV cured
size. Add the specimen dropwise, shaking values in a set is less than or equal to coating or ink, use the following
(swirling) the dish to disperse the specimen the intra-laboratory precision statement equation:
completely in the solvent. If the material in Section 13.1.
forms a lump that cannot be dispersed, 11.3.2.2 Record the arithmetic C = F A Dc Eq. 24-1
discard the specimen and prepare a new one. average (ww).
Similarly, prepare a duplicate. The sample 11.3.3 Coating Density. Determine 12.3 Calculate Wv for each analysis
shall stand for a minimum of 1 hour, but no the density (Dc, kg/l) of the surface as shown below:
more than 24 hours prior to being oven cured
coating using the procedure in ASTM D
at 110 ± 5°C (230 ± 9°F) for 1 hour. W1 − W2
11.2.2.2 Heat the aluminum foil
1475. Wv = Eq. 24-2
11.3.3.1 Run duplicate analyses W3
dishes containing the dispersed until each value in a set deviates from
specimens in the forced draft oven for 12.4 Nonaqueous Volatile Matter.
the mean of the set by no more than the 12.4.1 Solvent-borne Coatings.
60 min at 110 ± 5°C (230 ± 9°F). intra-laboratory precision statement in
Caution—provide adequate ventilation, Section 13.1. Wo = Wv Eq. 24-3
consistent with accepted laboratory 11.3.3.2 Record the arithmetic
practice, to prevent solvent vapors from 12.4.2 Waterborne Coatings.
average (Dc).
accumulating to a dangerous level.
11.2.2.3 Remove the dishes from the
11.3.4 Solids Content. Determine the Wo = Wv − Ww Eq. 24-4
volume fraction (Vs) solids of the
oven, place immediately in a desiccator, coating by calculation using the 12.4.3 Coatings Containing Exempt
cool to ambient temperature, and weigh manufacturer’s formulation. Solvents.
to within 1 mg. 11.3.5 Exempt Solvent Content.
11.2.2.4 Run analyses in pairs Wo = Wv − WE − Ww Eq. 24-5
Determine the weight fraction of exempt
(duplicate sets) for each coating mixture 12.5 Weight Fraction Solids.
solvents (WE) by using ASTM Method
until the criterion in Section 11.4 is met.
D4457. Run a duplicate set of
Calculate WV following Equation 24–2
determinations and record the Ws = 1 − Wv Eq. 24-6
and record the arithmetic average.
11.2.3 Water Content. To determine arithmetic average (WE). 12.6 Confidence Limit Calculations
water content, follow Section 11.3.2. 11.4 Sample Analysis Criteria. For for Waterborne Coatings. To calculate
11.2.4 Coating Density. To Wv and Ww, run duplicate analyses until the lower confidence limit, subtract the
determine coating density, follow the difference between the two values in appropriate inter-laboratory precision
Section 11.3.3. a set is less than or equal to the intra- value from the measured mean value for
11.2.5 Solids Content. To determine laboratory precision statement for that that parameter. To calculate the upper
solids content, follow Section 11.3.4. parameter. For Dc, run duplicate confidence limit, add the appropriate
11.2.6 Exempt Solvent Content. To analyses until each value in a set inter-laboratory precision value to the
determine the exempt solvent content, deviates from the mean of the set by no measured mean value for that
follow Section 11.3.5. more than the intra-laboratory precision parameter. For Wv and Dc, use the lower
Note: For all other coatings (i.e., water-or statement. If, after several attempts, it is confidence limits; for Ww, use the upper
solvent-borne coatings) not covered by concluded that the ASTM procedures confidence limit. Because Ws is
multicomponent or UV radiation-cured cannot be used for the specific coating calculated, there is no adjustment for
coatings, analyze as shown below: with the established intra-laboratory this parameter.

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