[[pp. 61993-62042]] Amendments for Testing and Monitoring Provisions

Note: EPA no longer updates this information, but it may be useful as a reference or resource.

[Federal Register: October 17, 2000 (Volume 65, Number 201)]
[Rules and Regulations]
[Page 61993-62042]
From the Federal Register Online via GPO Access [wais.access.gpo.gov]
[DOCID:fr17oc00-15]

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the original endpoint was in error. It is recommended that persons
conducting this test perform several titrations to be able to
correctly identify the endpoint. The importance of this should be
recognized because the results of this analytical procedure are
extremely sensitive to errors in titration.

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

Bwa = Fraction of water vapor in ambient air during orifice
calibration.
CH2S = H2S concentration in cylinder
gas, ppmv.
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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 deg.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, deg.K.
Tstd = Standard absolute temperature, 293 deg.K.
s = Sampling time, min.
sb = 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).
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16.13.3 Normality of Standard Iodine Solution (0.01 N).
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16.13.4 Sample Gas Volume.
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16.13.5 Concentration of H2S in the Gas Cylinder.

17.0 References
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1. American Public Health Association, American Water Works
Association, and Water Pollution Control Federation. Standard
Methods for the Examination of Water and Wastewater. Washington, DC.
American Public Health Association. 1975. pp. 316-317.
2. American Society for Testing and Materials. Annual Book of
ASTM Standards. Part 31: Water, Atmospheric Analysis. Philadelphia,
PA. 1974. pp. 40-42.
3. Blosser, R.O. A Study of TRS Measurement Methods. National
Council of the Paper Industry for Air and Stream Improvement, Inc.,
New York, NY. Technical Bulletin No. 434. May 1984. 14 pp.
4. Blosser, R.O., H.S. Oglesby, and A.K. Jain. A Study of
Alternate SO2 Scrubber Designs Used for TRS Monitoring. A
Special Report by the National Council of the Paper Industry for Air
and Stream Improvement, Inc., New York, NY. July 1977.
5. Curtis, F., and G.D. McAlister. Development and Evaluation of
an Oxidation/Method 6 TRS Emission Sampling Procedure. Emission
Measurement Branch, Emission Standards and Engineering Division,
U.S. Environmental Protection Agency, Research Triangle Park, NC
27711. February 1980.
6. Gellman, I. A Laboratory and Field Study of Reduced Sulfur
Sampling and Monitoring Systems. National Council of the Paper
Industry for Air and Stream Improvement, Inc., New York, NY.
Atmospheric Quality Improvement Technical Bulletin No. 81. October
1975.
7. Margeson, J.H., J.E. Knoll, and M.R. Midgett. A Manual Method
for TRS Determination. Source Branch, Quality Assurance Division,
U.S. Environmental Protection Agency, Research Triangle Park, NC
27711.
8. National Council of the Paper Industry for Air and Stream
Improvement. An Investigation of H2S and SO2.
Calibration Cylinder Gas Stability and Their Standardization Using
Wet Chemical Techniques. Special Report 76-06. New York, NY. August
1976.
9. National Council of the Paper Industry for Air and Stream
Improvement. Wet Chemical Method for Determining the H2S
Concentration of Calibration Cylinder Gases. Technical Bulletin
Number 450. New York, NY. January 1985. 23 pp.
10. National Council of the Paper Industry for Air and Stream
Improvement. Modified Wet Chemical Method for Determining the
H2S Concentration of Calibration Cylinder Gases. Draft
Report. New York, NY. March 1987. 29 pp.
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18.0 Tables, Diagrams, Flowcharts, and Validation Data
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Date------------------------------------------------------------------
Critical orifice ID---------------------------------------------------
Soap bubble meter volume, Vsb____ liters
Time, sb
Run no. 1 ____ min ____ sec
Run no. 2 ____ min ____ sec
Run no. 3 ____ min ____ sec
Average ____ min ____ sec
Covert the seconds to fraction of minute:
Time = ____ min + ____ Sec/60 = ____ min
Barometric pressure, Pbar = ____ mm Hg
Ambient temperature, t amb = 273 + ____ deg.C = ____
deg.K = ____ mm Hg. (This should be approximately 0.4 times
barometric pressure.)
Pump vacuum,
[GRAPHIC] [TIFF OMITTED] TR17OC00.298

Table 16A-1. Critical Orifice Calibration Data

Method 16B--Determination of Total Reduced Sulfur Emissions From
Stationary Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., 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 applicable for determining TRS
emissions from recovery furnaces (boilers), lime kilns, and smelt
dissolving tanks at kraft pulp mills, and from other sources when
specified in an applicable subpart of the regulations. The flue gas
must contain at least 1 percent oxygen for complete oxidation of all
TRS to SO2.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 An integrated gas sample is extracted from the stack. The
SO2 is removed selectively from the sample using a citrate
buffer solution. The TRS compounds are then thermally oxidized to
SO2 and analyzed as SO2 by gas chromatography
(GC) using flame photometric detection (FPD).

3.0 Definitions. [Reserved]

4.0 Interferences

4.1 Reduced sulfur compounds other than those regulated by the
emission standards, if present, may be measured by this method.
Therefore, carbonyl sulfide, which is partially oxidized to
SO2 and may be present in a lime kiln exit stack, would be a
positive interferant.
4.2 Particulate matter from the lime kiln stack gas (primarily
calcium carbonate) can cause a negative bias if it is allowed to enter
the citrate scrubber; the particulate matter will cause the pH to rise
and H2S to be absorbed before oxidation. Proper use of the
particulate filter, described in Section 6.1.3 of Method 16A, will
eliminate this interference.
4.3 Carbon monoxide (CO) and carbon dioxide (CO2) have
substantial desensitizing effects on the FPD even after dilution.
Acceptable systems must demonstrate that they have eliminated this
interference by some procedure such as eluting these compounds before
the SO2. Compliance with this requirement can be
demonstrated by submitting chromatograms of calibration gases with and
without CO2 in diluent gas. The CO2 level should
be approximately 10 percent for the case with CO2 present.
The two chromatograms should show agreement within the precision limits
of Section 13.0.

5.0 Safety

5.1 Disclaimer. This method may involve hazardous materials,
operations, and equipment. This test method may not address all of the
safety problems associated with its use. It is the

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responsibility of the user of this test method to establish appropriate
safety and health practices and determine the applicability of
regulatory limitations prior to performing this test method.
5.2 Hydrogen Sulfide (H2S). A flammable, poisonous gas
with the odor of rotten eggs. H2S is extremely hazardous and
can cause collapse, coma, and death within a few seconds of one or two
inhalations at sufficient concentrations. Low concentrations irritate
the mucous membranes and may cause nausea, dizziness, and headache
after exposure.

6.0 Equipment and Supplies

6.1 Sample Collection. The sampling train is shown in Figure 16B-
1. Modifications to the apparatus are accepted provided the system
performance check in Section 8.4.1 is met.
6.1.1 Probe, Probe Brush, Particulate Filter, SO2
Scrubber, Combustion Tube, and Furnace. Same as in Method 16A, Sections
6.1.1 to 6.1.6.
6.1.2 Sampling Pump. Leakless Teflon-coated diaphragm type or
equivalent.
6.2 Analysis.
6.2.1 Dilution System (optional), Gas Chromatograph, Oven,
Temperature Gauges, Flow System, Flame Photometric Detector,
Electrometer, Power Supply, Recorder, Calibration System, Tube Chamber,
Flow System, and Constant Temperature Bath. Same as in Method 16,
Sections 6.2.1, 6.2.2, and 6.3.
6.2.2 Gas Chromatograph Columns. Same as in Method 16, Section
6.2.3. Other columns with demonstrated ability to resolve
SO2 and be free from known interferences are acceptable
alternatives. Single column systems such as a 7-ft Carbsorb B HT 100
column have been found satisfactory in resolving SO2 from
CO2.

7.0 Reagents and Standards

Same as in Method 16, Section 7.0, except for the following:
7.1 Calibration Gas. SO2 permeation tube
gravimetrically calibrated and certified at some convenient operating
temperature. These tubes consist of hermetically sealed FEP Teflon
tubing in which a liquefied gaseous substance is enclosed. The enclosed
gas permeates through the tubing wall at a constant rate. When the
temperature is constant, calibration gases covering a wide range of
known concentrations can be generated by varying and accurately
measuring the flow rate of diluent gas passing over the tubes. In place
of SO2 permeation tubes, cylinder gases containing
SO2 in nitrogen may be used for calibration. The cylinder
gas concentration must be verified according to Section 8.2.1 of Method
6C. The calibration gas is used to calibrate the GC/FPD system and the
dilution system.
7.2 Recovery Check Gas.
7.2.1 Hydrogen sulfide [100 parts per million by volume (ppmv) or
less] in nitrogen, stored in aluminum cylinders. Verify the
concentration by Method 11, the procedure discussed in Section 16.0 of
Method 16A, or gas chromatography where the instrument is calibrated
with an H2S permeation tube as described below. For the wet-
chemical methods, the standard deviation should not exceed 5 percent on
at least three 20-minute runs.
7.2.2 Hydrogen sulfide recovery gas generated from a permeation
device gravimetrically calibrated and certified at some convenient
operation temperature may be used. The permeation rate of the device
must be such that at a dilution gas flow rate of 3 liters/min (64
ft\3\/hr), an H2S concentration in the range of the stack
gas or within 20 percent of the emission standard can be generated.
7.3 Combustion Gas. Gas containing less than 50 ppbv reduced
sulfur compounds and less than 10 ppmv total hydrocarbons. The gas may
be generated from a clean-air system that purifies ambient air and
consists of the following components: diaphragm pump, silica gel drying
tube, activated charcoal tube, and flow rate measuring device. Gas from
a compressed air cylinder is also acceptable.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Pretest Procedures. Same as in Method 15, Section 8.1.
8.2 Sample Collection. Before any source sampling is performed,
conduct a system performance check as detailed in Section 8.4.1 to
validate the sampling train components and procedures. Although this
test is optional, it would significantly reduce the possibility of
rejecting tests as a result of failing the post-test performance check.
At the completion of the pretest system performance check, insert the
sampling probe into the test port making certain that no dilution air
enters the stack though the port. Condition the entire system with
sample for a minimum of 15 minutes before beginning analysis. If the
sample is diluted, determine the dilution factor as in Section 10.4 of
Method 15.
8.3 Analysis. Inject aliquots of the sample into the GC/FPD
analyzer for analysis. Determine the concentration of SO2
directly from the calibration curves or from the equation for the
least-squares line.
8.4. Post-Test Procedures
8.4.1 System Performance Check. Same as in Method 16A, Section
8.5. A sufficient number of sample injections should be made so that
the precision requirements of Section 13.2 are satisfied.
8.4.2 Determination of Calibration Drift. Same as in Method 15,
Section 8.3.2.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.2, 8.3...................... System Ensure validity of
performance sampling train
check. components and
analytical
procedure.
8.1........................... Sampling Ensure accurate
equipment leak- measurement of stack
check and gas flow rate,
calibration. sample volume.
10.0.......................... Analytical Ensure precision of
calibration. 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.

[[Page 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.
[GRAPHIC] [TIFF OMITTED] TR17OC00.299

12.4 Average TRS Concentration
[GRAPHIC] [TIFF OMITTED] TR17OC00.300

13.0 Method Performance.

13.1 Range and Sensitivity. Coupled with a GC using a 1-ml sample
size, the maximum limit of the FPD for SO2 is approximately
10 ppmv. This limit is extended by diluting the sample gas before
analysis or by reducing the sample aliquot size. For sources with
emission levels between 10 and 100 ppm, the measuring range can be best
extended by reducing the sample size.
13.2 GC/FPD Calibration and Precision. A series of three
consecutive injections of the sample calibration gas, at any dilution,
must produce results which do not vary by more than 5 percent from the
mean of the three injections.
13.3 Calibration Drift. The calibration drift determined from the
mean of the three injections made at the beginning and end of any run
or series of runs within a 24-hour period must not exceed 5 percent.
13.4 System Calibration Accuracy. Losses through the sample
transport system must be measured and a correction factor developed to
adjust the calibration accuracy to 100 percent.
13.5 Field tests between this method and Method 16A showed an
average difference of less than 4.0 percent. This difference was not
determined to be significant.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. Same as in Method 16, Section 16.0.
2. National Council of the Paper Industry for Air and Stream
Improvement, Inc, A Study of TRS Measurement Methods. Technical
Bulletin No. 434. New York, NY. May 1984. 12p.
3. Margeson, J.H., J.E. Knoll, and M.R. Midgett. A Manual Method
for TRS Determination. Draft available from the authors. Source
Branch, Quality Assurance Division, U.S. Environmental Protection
Agency, Research Triangle Park, NC 27711.
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17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.301

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Method 17--Determination of Particulate Matter Emissions From
Stationary Sources

Note: This method does not include all of the specifications
(e.g., equipment and supplies) and procedures (e.g., 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 thorough knowledge of at least the following
additional test methods: Method 1, Method 2, Method 3, Method 5.

1.0 Scope and Application

1.1 Analyte. Particulate matter (PM). No CAS number assigned.

Note: Particulate matter is not an absolute quantity. It is a
function of temperature and pressure. Therefore, to prevent
variability in PM emission regulations and/or associated test
methods, the temperature and pressure at which PM is to be measured
must be carefully defined. Of the two variables (i.e., temperature
and pressure), temperature has the greater effect upon the amount of
PM in an effluent gas stream; in most stationary source categories,
the effect of pressure appears to be negligible. In Method 5, 120
deg.C (248 deg.F) is established as a nominal reference
temperature. Thus, where Method 5 is specified in an applicable
subpart of the standard, PM is defined with respect to temperature.
In order to maintain a collection temperature of 120 deg.C (248
deg.F), Method 5 employs a heated glass sample probe and a heated
filter holder. This equipment is somewhat cumbersome and requires
care in its operation. Therefore, where PM concentrations (over the
normal range of temperature associated with a specified source
category) are known to be independent of temperature, it is
desirable to eliminate the glass probe and the heating systems, and
to sample at stack temperature.

1.2 Applicability. This method is applicable for the determination
of PM emissions, where PM concentrations are known to be independent of
temperature over the normal range of temperatures characteristic of
emissions from a specified source category. It is intended to be used
only when specified by an applicable subpart of the standards, and only
within the applicable temperature limits (if specified), or when
otherwise approved by the Administrator. This method is not applicable
to stacks that contain liquid droplets or are saturated with water
vapor. In addition, this method shall not be used as written if the
projected cross-sectional area of the probe extension-filter holder
assembly covers more than 5 percent of the stack cross-sectional area
(see Section 8.1.2).
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 Particulate matter is withdrawn isokinetically from the source
and collected on a glass fiber filter maintained at stack temperature.
The PM mass is determined gravimetrically after the removal of
uncombined water.

3.0 Definitions

Same as Method 5, Section 3.0.

4.0 Interferences. [Reserved]

5.0 Safety

6.0 Equipment and Supplies

6.1 Sampling Train. A schematic of the sampling train used in this
method is shown in Figure 17-1. The sampling train components and
operation and maintenance are very similar to Method 5, which should be
consulted for details.
6.1.1 Probe Nozzle, Differential Pressure Gauge, Metering System,
Barometer, Gas Density Determination Equipment. Same as in Method 5,
Sections 6.1.1, 6.1.4, 6.1.8, 6.1.9, and 6.1.10, respectively.
6.1.2 Filter Holder. The in-stack filter holder shall be
constructed of borosilicate or quartz glass, or stainless steel. If a
gasket is used, it shall be made of silicone rubber, Teflon, or
stainless steel. Other holder and gasket materials may be used, subject
to the approval of the Administrator. The filter holder shall be
designed to provide a positive seal against leakage from the outside or
around the filter.
6.1.3 Probe Extension. Any suitable rigid probe extension may be
used after the filter holder.
6.1.4 Pitot Tube. Same as in Method 5, Section 6.1.3.
6.1.4.1 It is recommended (1) that the pitot tube have a known
baseline coefficient, determined as outlined in Section 10 of Method 2;
and (2) that this known coefficient be preserved by placing the pitot
tube in an interference-free arrangement with respect to the sampling
nozzle, filter holder, and temperature sensor (see Figure 17-1). Note
that the 1.9 cm (\3/4\-in.) free-space between the nozzle and pitot
tube shown in Figure 17-1, is based on a 1.3 cm (\1/2\-in.) ID nozzle.
If the sampling train is designed for sampling at higher flow rates
than that described in APTD-0581, thus necessitating the use of larger
sized nozzles, the free-space shall be 1.9 cm (\3/4\-in.) with the
largest sized nozzle in place.
6.1.4.2 Source-sampling assemblies that do not meet the minimum
spacing requirements of Figure 17-1 (or the equivalent of these
requirements, e.g., Figure 2-4 of Method 2) may be used; however, the
pitot tube coefficients of such assemblies shall be determined by
calibration, using methods subject to the approval of the
Administrator.
6.1.5 Condenser. It is recommended that the impinger system or
alternatives described in Method 5 be used to determine the moisture
content of the stack gas. Flexible tubing may be used between the probe
extension and condenser. Long tubing lengths may affect the moisture
determination.
6.2 Sample Recovery. Probe-liner and probe-nozzle brushes, wash
bottles, glass sample storage containers, petri dishes, graduated
cylinder and/or balance, plastic storage containers, funnel and rubber
policeman, funnel. Same as in Method 5, Sections 6.2.1 through 6.2.8,
respectively.
6.3 Sample Analysis. Glass weighing dishes, desiccator, analytical
balance, balance, beakers, hygrometer, temperature sensor. Same as in
Method 5, Sections 6.3.1 through 6.3.7, respectively.

7.0 Reagents and Standards

7.1 Sampling. Filters, silica gel, water, crushed ice, stopcock
grease. Same as in Method 5, Sections 7.1.1, 7.1.2, 7.1.3, 7.1.4, and
7.1.5, respectively. Thimble glass fiber filters may also be used.
7.2 Sample Recovery. Acetone (reagent grade). Same as in Method 5,
Section 7.2.
7.3 Sample Analysis. Acetone and Desiccant. Same as in Method 5,
Sections 7.3.1 and 7.3.2, respectively.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Sampling.
8.1.1 Pretest Preparation. Same as in Method 5, Section 8.1.1.
8.1.2 Preliminary Determinations. Same as in Method 5, Section
8.1.2, except as follows: Make a projected-area model of the probe
extension-filter holder assembly, with the pitot tube face openings
positioned along the centerline of the stack, as shown in Figure 17-2.
Calculate the estimated cross-section blockage, as shown in Figure 17-
2. If the blockage exceeds 5 percent of the duct cross sectional area,
the tester has the following options exist: (1) a suitable out-of-stack
filtration

[[Page 62004]]

method may be used instead of in-stack filtration; or (2) a special in-
stack arrangement, in which the sampling and velocity measurement sites
are separate, may be used; for details concerning this approach,
consult with the Administrator (see also Reference 1 in Section 17.0).
Select a probe extension length such that all traverse points can be
sampled. For large stacks, consider sampling from opposite sides of the
stack to reduce the length of probes.
8.1.3 Preparation of Sampling Train. Same as in Method 5, Section
8.1.3, except the following: Using a tweezer or clean disposable
surgical gloves, place a labeled (identified) and weighed filter in the
filter holder. Be sure that the filter is properly centered and the
gasket properly placed so as not to allow the sample gas stream to
circumvent the filter. Check filter for tears after assembly is
completed. Mark the probe extension with heat resistant tape or by some
other method to denote the proper distance into the stack or duct for
each sampling point. Assemble the train as in Figure 17-1, using a very
light coat of silicone grease on all ground glass joints and greasing
only the outer portion (see APTD-0576) to avoid possibility of
contamination by the silicone grease. Place crushed ice around the
impingers.
8.1.4 Leak-Check Procedures. Same as in Method 5, Section 8.1.4,
except that the filter holder is inserted into the stack during the
sampling train leak-check. To do this, plug the inlet to the probe
nozzle with a material that will be able to withstand the stack
temperature. Insert the filter holder into the stack and wait
approximately 5 minutes (or longer, if necessary) to allow the system
to come to equilibrium with the temperature of the stack gas stream.
8.1.5 Sampling Train Operation. The operation is the same as in
Method 5. Use a data sheet such as the one shown in Figure 5-3 of
Method 5, except that the filter holder temperature is not recorded.
8.1.6 Calculation of Percent Isokinetic. Same as in Method 5,
Section 12.11.
8.2 Sample Recovery.
8.2.1 Proper cleanup procedure begins as soon as the probe
extension assembly is removed from the stack at the end of the sampling
period. Allow the assembly to cool.
8.2.2 When the assembly can be safely handled, wipe off all
external particulate matter near the tip of the probe nozzle and place
a cap over it to prevent losing or gaining particulate matter. Do not
cap off the probe tip tightly while the sampling train is cooling down
as this would create a vacuum in the filter holder, forcing condenser
water backward.
8.2.3 Before moving the sample train to the cleanup site,
disconnect the filter holder-probe nozzle assembly from the probe
extension; cap the open inlet of the probe extension. Be careful not to
lose any condensate, if present. Remove the umbilical cord from the
condenser outlet and cap the outlet. If a flexible line is used between
the first impinger (or condenser) and the probe extension, disconnect
the line at the probe extension and let any condensed water or liquid
drain into the impingers or condenser. Disconnect the probe extension
from the condenser; cap the probe extension outlet. After wiping off
the silicone grease, cap off the condenser inlet. Ground glass
stoppers, plastic caps, or serum caps (whichever are appropriate) may
be used to close these openings.
8.2.4 Transfer both the filter holder-probe nozzle assembly and
the condenser to the cleanup area. This area should be clean and
protected from the wind so that the chances of contaminating or losing
the sample will be minimized.
8.2.5 Save a portion of the acetone used for cleanup as a blank.
Take 200 ml of this acetone from the wash bottle being used and place
it in a glass sample container labeled ``acetone blank.'' Inspect the
train prior to and during disassembly and not any abnormal conditions.
Treat the sample as discussed in Method 5, Section 8.2.

9.0 Quality Control. [Reserved]

10.0 Calibration and Standardization

The calibrations of the probe nozzle, pitot tube, metering system,
temperature sensors, and barometer are the same as in Method 5,
Sections 10.1 through 10.3, 10.5, and 10.6, respectively.

11.0 Analytical Procedure

Same as in Method 5, Section 11.0. Analytical data should be
recorded on a form similar to that shown in Figure 5-6 of Method 5.

12.0 Data Analysis and Calculations.

Same as in Method 5, Section 12.0.

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 Alternative Procedures

Same as in Method 5, Section 16.0.

17.0 References

Same as in Method 5, Section 17.0, with the addition of the
following:

1. Vollaro, R.F. Recommended Procedure for Sample Traverses in
Ducts Smaller than 12 Inches in Diameter. U.S. Environmental
Protection Agency, Emission Measurement Branch. Research Triangle
Park, NC. November 1976.
BILLING CODE 6560-50-P

[[Page 62005]]

18.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.302

[[Page 62006]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.303

BILLING CODE 6560-50-C

[[Page 62007]]

Method 18--Measurement of Gaseous Organic Compound Emissions By Gas
Chromatography

Note:
This method is not inclusive with respect to specifications
(e.g., equipment and supplies) and procedures (e.g., 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 thorough knowledge of at least the following
additional test methods: Method 1, Method 2, Method 3.

Note:
This method should not be attempted by persons unfamiliar with
the performance characteristics of gas chromatography, nor by those
persons who are unfamiliar with source sampling. Particular care
should be exercised in the area of safety concerning choice of
equipment and operation in potentially explosive atmospheres.

1.0 Scope and Application

1.1 Analyte. Total gaseous organic compounds.
1.2 Applicability.
1.2.1 This method is designed to measure gaseous organics emitted
from an industrial source. While designed for ppm level sources, some
detectors are quite capable of detecting compounds at ambient levels,
e.g., ECD, ELCD, and helium ionization detectors. Some other types of
detectors are evolving such that the sensitivity and applicability may
well be in the ppb range in only a few years.
1.2.2 This method will not determine compounds that (1) are
polymeric (high molecular weight), (2) can polymerize before analysis,
or (3) have very low vapor pressures at stack or instrument conditions.
1.3 Range. The lower range of this method is determined by the
sampling system; adsorbents may be used to concentrate the sample, thus
lowering the limit of detection below the 1 part per million (ppm)
typically achievable with direct interface or bag sampling. The upper
limit is governed by GC detector saturation or column overloading; the
upper range can be extended by dilution of sample with an inert gas or
by using smaller volume gas sampling loops. The upper limit can also be
governed by condensation of higher boiling compounds.
1.4 Sensitivity. The sensitivity limit for a compound is defined
as the minimum detectable concentration of that compound, or the
concentration that produces a signal-to-noise ratio of three to one.
The minimum detectable concentration is determined during the presurvey
calibration for each compound.

2.0 Summary of Method

The major organic components of a gas mixture are separated by gas
chromatography (GC) and individually quantified by flame ionization,
photoionization, electron capture, or other appropriate detection
principles. The retention times of each separated component are
compared with those of known compounds under identical conditions.
Therefore, the analyst confirms the identity and approximate
concentrations of the organic emission components beforehand. With this
information, the analyst then prepares or purchases commercially
available standard mixtures to calibrate the GC under conditions
identical to those of the samples. The analyst also determines the need
for sample dilution to avoid detector saturation, gas stream filtration
to eliminate particulate matter, and prevention of moisture
condensation.

3.0 Definitions. [Reserved]

4.0 Interferences

4.1 Resolution interferences that may occur can be eliminated by
appropriate GC column and detector choice or by shifting the retention
times through changes in the column flow rate and the use of
temperature programming.
4.2 The analytical system is demonstrated to be essentially free
from contaminants by periodically analyzing blanks that consist of
hydrocarbon-free air or nitrogen.
4.3 Sample cross-contamination that occurs when high-level and
low-level samples or standards are analyzed alternately is best dealt
with by thorough purging of the GC sample loop between samples.
4.4 To assure consistent detector response, calibration gases are
contained in dry air. To adjust gaseous organic concentrations when
water vapor is present in the sample, water vapor concentrations are
determined for those samples, and a correction factor is applied.
4.5 The gas chromatograph run time must be sufficient to clear all
eluting peaks from the column before proceeding to the next run (in
order to prevent sample carryover).

5.0 Safety

6.0 Equipment and Supplies

6.1 Equipment needed for the presurvey sampling procedure can be
found in Section 16.1.1.
6.2 Equipment needed for the integrated bag sampling and analysis
procedure can be found in Section 8.2.1.1.1.
6.3 Equipment needed for direct interface sampling and analysis
can be found in Section 8.2.2.1.
6.4 Equipment needed for the dilution interface sampling and
analysis can be found in Section 8.2.3.1.
6.5 Equipment needed for adsorbent tube sampling and analysis can
be found in Section 8.2.4.1.

7.0 Reagents and Standards

7.1 Reagents needed for the presurvey sampling procedure can be
found in Section 16.1.2.
7.2 Quality Assurance Audit Samples. When making compliance
determinations, and upon availability, an audit sample may be obtained
from the appropriate EPA Regional Office or from the responsible
enforcement authority.

Note: The responsible enforcement autority should be notified at
least 30 days prior to the test date to allow sufficient time for
sample delivery.

8.0 Sample Collection, Preservation, Storage, and Transport

8.2 Final Sampling and Analysis Procedure. Considering safety
(flame hazards) and the source conditions, select an appropriate
sampling and analysis procedure (Section 8.2.1, 8.2.2, 8.2.3 or 8.2.4).
In situations where a hydrogen flame is a hazard and no intrinsically
safe GC is suitable, use the flexible bag collection technique or an
adsorption technique.
8.2.1 Integrated Bag Sampling and Analysis.
8.2.1.1 Evacuated Container Sampling Procedure. In this procedure,
the bags are filled by evacuating the rigid air-tight container holding
the bags. Use a field sample data sheet as shown in Figure 18-10.
Collect triplicate samples from each sample location.
8.2.1.1.1 Apparatus.
8.2.1.1.1.1 Probe. Stainless steel, Pyrex glass, or Teflon tubing
probe, according to the duct temperature, with Teflon tubing of
sufficient length to connect to the sample bag. Use stainless

[[Page 62008]]

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

[[Page 62009]]

to all safety requirements with this method.
8.2.2.1 Apparatus.
8.2.2.1.1 Probe. Constructed of stainless steel, Pyrex glass, or
Teflon tubing as dictated by duct temperature and reactivity of target
compounds. A filter or glass wool plug may be needed if particulate is
present in the stack gas. If necessary, heat the probe with heating
tape or a special heating unit capable of maintaining a temperature
greater than 110 deg.C.
8.2.2.1.2 Sample Lines. 6.4-mm OD (or other diameter as needed)
Teflon lines, heat-traced to prevent condensation of material (greater
than 110 deg.C).
8.2.2.1.3 Quick Connects. To connect sample line to gas sampling
valve on GC instrument and to pump unit used to withdraw source gas.
Use a quick connect or equivalent on the cylinder or bag containing
calibration gas to allow connection of the calibration gas to the gas
sampling valve.
8.2.2.1.4 Thermocouple Readout Device. Potentiometer or digital
thermometer, to measure source temperature and probe temperature.
8.2.2.1.5 Heated Gas Sampling Valve. Of two-position, six-port
design, to allow sample loop to be purged with source gas or to direct
source gas into the GC instrument.
8.2.2.1.6 Needle Valve. To control gas sampling rate from the
source.
8.2.2.1.7 Pump. Leakless Teflon-coated diaphragm-type pump or
equivalent, capable of at least 1 liter/minute sampling rate.
8.2.2.1.8 Flowmeter. Of suitable range to measure sampling rate.
8.2.2.1.9 Charcoal Adsorber. To adsorb organic vapor vented from
the source to prevent exposure of personnel to source gas.
8.2.2.1.10 Gas Cylinders. Carrier gas, oxygen and fuel as needed
to run GC and detector.
8.2.2.1.11 Gas Chromatograph. Capable of being moved into the
field, with detector, heated gas sampling valve, column required to
complete separation of desired components, and option for temperature
programming.
8.2.2.1.12 Recorder/Integrator. To record results.
8.2.2.2 Procedure. Calibrate the GC using the procedures in
Section 8.2.1.5.2.1. To obtain a stack gas sample, assemble the
sampling system as shown in Figure 18-12. Make sure all connections are
tight. Turn on the probe and sample line heaters. As the temperature of
the probe and heated line approaches the target temperature as
indicated on the thermocouple readout device, control the heating to
maintain a temperature greater than 110 deg.C. Conduct a 3-point
calibration of the GC by analyzing each gas mixture in triplicate.
Generate a calibration curve. Place the inlet of the probe at the
centroid of the duct, or at a point no closer to the walls than 1 m,
and draw source gas into the probe, heated line, and sample loop. After
thorough flushing, analyze the stack gas sample using the same
conditions as for the calibration gas mixture. For each run, sample,
analyze, and record five consecutive samples. A test consists of three
runs (five samples per run times three runs, for a total of fifteen
samples). After all samples have been analyzed, repeat the analysis of
the mid-level calibration gas for each compound. For each calibration
standard, compare the pre- and post-test average response factors (RF)
for each compound. If the two calibration RF values (pre- and post-
analysis) differ by more than 5 percent from their mean value, then
analyze the other calibration gas levels for that compound and
determine the stack gas sample concentrations by comparison to both
calibration curves (this is done by preparing a calibration curve using
all the pre and post-test calibration gas mixture values). If the two
calibration RF values differ by less than 5 percent from their mean
value, the tester has the option of using only the pre-test calibration
curve to generate the concentration values. Record this calibration
data and the other required data on the data sheet shown in Figure 18-
11, deleting the dilution gas information.

Note: Take care to draw all samples, calibration mixtures, and
audits through the sample loop at the same pressure.

8.2.2.3 Determination of Stack Gas Moisture Content. Use Method 4
to measure the stack gas moisture content.
8.2.2.4 Quality Assurance. Same as Section 8.2.1.7. Introduce the
audit gases in the sample line immediately following the probe.
8.2.2.5 Emission Calculations. Same as Section 8.2.1.8.
8.2.3 Dilution Interface Sampling and Analysis Procedure. Source
samples that contain a high concentration of organic materials may
require dilution prior to analysis to prevent saturating the GC
detector. The apparatus required for this direct interface procedure is
basically the same as that described in the Section 8.2.2, except a
dilution system is added between the heated sample line and the gas
sampling valve. The apparatus is arranged so that either a 10:1 or
100:1 dilution of the source gas can be directed to the chromatograph.
A pump of larger capacity is also required, and this pump must be
heated and placed in the system between the sample line and the
dilution apparatus.
8.2.3.1 Apparatus. The equipment required in addition to that
specified for the direct interface system is as follows:
8.2.3.1.1 Sample Pump. Leakless Teflon-coated diaphragm-type that
can withstand being heated to 120 deg.C and deliver 1.5 liters/minute.
8.2.3.1.2 Dilution Pumps. Two Model A-150 Komhyr Teflon positive
displacement type delivering 150 cc/minute, or equivalent. As an
option, calibrated flowmeters can be used in conjunction with Teflon-
coated diaphragm pumps.
8.2.3.1.3 Valves. Two Teflon three-way valves, suitable for
connecting to Teflon tubing.
8.2.3.1.4 Flowmeters. Two, for measurement of diluent gas.
8.2.3.1.5 Diluent Gas with Cylinders and Regulators. Gas can be
nitrogen or clean dry air, depending on the nature of the source gases.
8.2.3.1.6 Heated Box. Suitable for being heated to 120 deg.C, to
contain the three pumps, three-way valves, and associated connections.
The box should be equipped with quick connect fittings to facilitate
connection of: (1) the heated sample line from the probe, (2) the gas
sampling valve, (3) the calibration gas mixtures, and (4) diluent gas
lines. A schematic diagram of the components and connections is shown
in Figure 18-13. The heated box shown in Figure 18-13 is designed to
receive a heated line from the probe. An optional design is to build a
probe unit that attaches directly to the heated box. In this way, the
heated box contains the controls for the probe heaters, or, if the box
is placed against the duct being sampled, it may be possible to
eliminate the probe heaters. In either case, a heated Teflon line is
used to connect the heated box to the gas sampling valve on the
chromatograph.

Note: Care must be taken to leak-check the system prior to the
dilutions so as not to create a potentially explosive atmosphere.

8.2.3.2 Procedure.
8.2.3.2.1 Assemble the apparatus by connecting the heated box,
shown in Figure 18-13, between the heated sample line from the probe
and the gas sampling valve on the chromatograph. Vent the source gas
from the gas sampling valve directly to the charcoal filter,
eliminating the pump and rotameter. Heat the sample probe, sample line,
and heated box. Insert the probe and source thermocouple at the
centroid of the duct, or to a point no closer to the walls than 1 m.
Measure the source temperature, and adjust all

[[Page 62010]]

heating units to a temperature 0 to 3 deg.C above this temperature. If
this temperature is above the safe operating temperature of the Teflon
components, adjust the heating to maintain a temperature high enough to
prevent condensation of water and organic compounds (greater than 110
deg.C). Calibrate the GC through the dilution system by following the
procedures in Section 8.2.1.5.2.1. Determine the concentration of the
diluted calibration gas using the dilution factor and the certified
concentration of the calibration gas. Record the pertinent data on the
data sheet shown in Figure 18-11.
8.2.3.2.2 Once the dilution system and GC operations are
satisfactory, proceed with the analysis of source gas, maintaining the
same dilution settings as used for the standards.
8.2.3.2.3 Analyze the audit samples using either the dilution
system, or directly connect to the gas sampling valve as required.
Record all data and report the results to the audit supervisor.
8.2.3.3 Determination of Stack Gas Moisture Content. Same as
Section 8.2.2.3.
8.2.3.4 Quality Assurance. Same as Section 8.2.2.4.
8.2.3.5 Emission Calculations. Same as section 8.2.2.5, with the
dilution factor applied.
8.2.4 Adsorption Tube Procedure. Any commercially available
adsorbent is allowed for the purposes of this method, as long as the
recovery study criteria in Section 8.4.3 are met. Help in choosing the
adsorbent may be found by calling the distributor, or the tester may
refer to National Institute for Occupational Safety and Health (NIOSH)
methods for the particular organics to be sampled. For some adsorbents,
the principal interferent will be water vapor. If water vapor is
thought to be a problem, the tester may place a midget impinger in an
ice bath before the adsorbent tubes. If this option is chosen, the
water catch in the midget impinger shall be analyzed for the target
compounds. Also, the spike for the recovery study (in Section 8.4.3)
shall be conducted in both the midget impinger and the adsorbent tubes.
The combined recovery (add the recovered amount in the impinger and the
adsorbent tubes to calculate R) shall then meet the criteria in Section
8.4.3.

Note: Post-test leak-checks are not allowed for this technique
since this can result in sample contamination.

8.2.4.1 Additional Apparatus. The following items (or equivalent)
are suggested.
8.2.4.1.1 Probe. Borosilicate glass or stainless steel,
approximately 6-mm ID, with a heating system if water condensation is a
problem, and a filter (either in-stack or out-of-stack, heated to stack
temperature) to remove particulate matter. In most instances, a plug of
glass wool is a satisfactory filter.
8.2.4.1.2 Flexible Tubing. To connect probe to adsorption tubes.
Use a material that exhibits minimal sample adsorption.
8.2.4.1.3 Leakless Sample Pump. Flow controlled, constant rate
pump, with a set of limiting (sonic) orifices.
8.2.4.1.4 Bubble-Tube Flowmeter. Volume accuracy within 1 percent,
to calibrate pump.
8.2.4.1.5 Stopwatch. To time sampling and pump rate calibration.
8.2.4.1.6 Adsorption Tubes. Precleaned adsorbent, with mass of
adsorbent to be determined by calculating breakthrough volume and
expected concentration in the stack.
8.2.4.1.7 Barometer. Accurate to 5 mm Hg, to measure atmospheric
pressure during sampling and pump calibration.
8.2.4.1.8 Rotameter. O to 100 cc/min, to detect changes in flow
rate during sampling.
8.2.4.2 Sampling and Analysis.
8.2.4.2.1 Calibrate the pump and limiting orifice flow rate
through adsorption tubes with the bubble tube flowmeter before
sampling. The sample system can be operated as a ``recirculating loop''
for this operation. Record the ambient temperature and barometric
pressure. Then, during sampling, use the rotameter to verify that the
pump and orifice sampling rate remains constant.
8.2.4.2.2 Use a sample probe, if required, to obtain the sample at
the centroid of the duct, or at a point no closer to the walls than 1
m. Minimize the length of flexible tubing between the probe and
adsorption tubes. Several adsorption tubes can be connected in series,
if the extra adsorptive capacity is needed. Adsorption tubes should be
maintained vertically during the test in order to prevent channeling.
Provide the gas sample to the sample system at a pressure sufficient
for the limiting orifice to function as a sonic orifice. Record the
total time and sample flow rate (or the number of pump strokes), the
barometric pressure, and ambient temperature. Obtain a total sample
volume commensurate with the expected concentration(s) of the volatile
organic(s) present, and recommended sample loading factors (weight
sample per weight adsorption media). Laboratory tests prior to actual
sampling may be necessary to predetermine this volume. If water vapor
is present in the sample at concentrations above 2 to 3 percent, the
adsorptive capacity may be severely reduced. Operate the gas
chromatograph according to the manufacturer's instructions. After
establishing optimum conditions, verify and document these conditions
during all operations. Calibrate the instrument. Analyze the audit
samples (see Section 16.1.4.3), then the emission samples.
8.2.4.3 Standards and Calibration. If using thermal desorption,
obtain calibration gases using the procedures in Section 10.1. If using
solvent extraction, prepare liquid standards in the desorption solvent.
Use a minimum of three different standards; select the concentrations
to bracket the expected average sample concentration. Perform the
calibration before and after each day's sample analyses using the
procedures in Section 8.2.1.5.2.1.
8.2.4.4 Quality Assurance.
8.2.4.4.1 Determine the recovery efficiency of the pollutants of
interest according to Section 8.4.3.
8.2.4.4.2 Determination of Sample Collection Efficiency
(Optional). If sample breakthrough is thought to be a problem, a
routine procedure for determining breakthrough is to analyze the
primary and backup portions of the adsorption tubes separately. If the
backup portion exceeds 10 percent of the total amount (primary and
back-up), it is usually a sign of sample breakthrough. For the purposes
of this method, only the recovery efficiency value (Section 8.4.3) is
used to determine the appropriateness of the sampling and analytical
procedure.
8.2.4.4.3 Volume Flow Rate Checks. Perform this check immediately
after sampling with all sampling train components in place. Use the
bubble-tube flowmeter to measure the pump volume flow rate with the
orifice used in the test sampling, and record the result. If it has
changed by more than 5 but less than 20 percent, calculate an average
flow rate for the test. If the flow rate has changed by more than 20
percent, recalibrate the pump and repeat the sampling.
8.2.4.4.4 Calculations. Correct all sample volumes to standard
conditions. If a sample dilution system has been used, multiply the
results by the appropriate dilution ratio. Correct all results
according to the applicable procedure in Section 8.4.3. Report results
as ppm by volume, dry basis.
8.3 Reporting of Results. At the completion of the field analysis
portion of the study, ensure that the data sheets shown in Figure 18-11
have been completed. Summarize this data on the data sheets shown in
Figure 18-15.
8.4 Recovery Study. After conducting the presurvey and

[[Page 62011]]

identifying all of the pollutants of interest, conduct the appropriate
recovery study during the test based on the sampling system chosen for
the compounds of interest.
8.4.1 Recovery Study for Direct Interface or Dilution Interface
Sampling. If the procedures in Section 8.2.2 or 8.2.3 are to be used to
analyze the stack gas, conduct the calibration procedure as stated in
Section 8.2.2.2 or 8.2.3.2, as appropriate. Upon successful completion
of the appropriate calibration procedure, attach the mid-level
calibration gas for at least one target compound to the inlet of the
probe or as close as possible to the inlet of the probe, but before the
filter. Repeat the calibration procedure by sampling and analyzing the
mid-level calibration gas through the entire sampling and analytical
system in triplicate. The mean of the calibration gas response sampled
through the probe shall be within 10 percent of the analyzer response.
If the difference in the two means is greater than 10 percent, check
for leaks throughout the sampling system and repeat the analysis of the
standard through the sampling system until this criterion is met.
8.4.2 Recovery Study for Bag Sampling.
8.4.2.1 Follow the procedures for the bag sampling and analysis in
Section 8.2.1. After analyzing all three bag samples, choose one of the
bag samples and tag this bag as the spiked bag. Spike the chosen bag
sample with a known mixture (gaseous or liquid) of all of the target
pollutants. The theoretical concentration, in ppm, of each spiked
compound in the bag shall be 40 to 60 percent of the average
concentration measured in the three bag samples. If a target compound
was not detected in the bag samples, the concentration of that compound
to be spiked shall be 5 times the limit of detection for that compound.
Store the spiked bag for the same period of time as the bag samples
collected in the field. After the appropriate storage time has passed,
analyze the spiked bag three times. Calculate the average fraction
recovered (R) of each spiked target compound with the equation in
Section 12.7.
8.4.2.2 For the bag sampling technique to be considered valid for
a compound, 0.70 R 1.30. If the R value does
not meet this criterion for a target compound, the sampling technique
is not acceptable for that compound, and therefore another sampling
technique shall be evaluated for acceptance (by repeating the recovery
study with another sampling technique). Report the R value in the test
report and correct all field measurements with the calculated R value
for that compound by using the equation in Section 12.8.
8.4.3 Recovery Study for Adsorption Tube Sampling. If following
the adsorption tube procedure in Section 8.2.4, conduct a recovery
study of the compounds of interest during the actual field test. Set up
two identical sampling trains. Collocate the two sampling probes in the
stack. The probes shall be placed in the same horizontal plane, where
the first probe tip is 2.5 cm from the outside edge of the other. One
of the sampling trains shall be designated the spiked train and the
other the unspiked train. Spike all of the compounds of interest (in
gaseous or liquid form) onto the adsorbent tube(s) in the spiked train
before sampling. The mass of each spiked compound shall be 40 to 60
percent of the mass expected to be collected with the unspiked train.
Sample the stack gas into the two trains simultaneously. Analyze the
adsorbents from the two trains utilizing identical analytical
procedures and instrumentation. Determine the fraction of spiked
compound recovered (R) using the equations in Section 12.9.
8.4.3.1 Repeat the procedure in Section 8.4.3 twice more, for a
total of three runs. In order for the adsorbent tube sampling and
analytical procedure to be acceptable for a compound,
0.70R1.30 (R in this case is the average of three
runs). If the average R value does not meet this criterion for a target
compound, the sampling technique is not acceptable for that compound,
and therefore another sampling technique shall be evaluated for
acceptance (by repeating the recovery study with another sampling
technique). Report the R value in the test report and correct all field
measurements with the calculated R value for that compound by using the
equation in Section 12.8.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures

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

9.2 Quality Assurance for Laboratory Procedures. Immediately after
the preparation of the calibration curves, the analysis audit described
in 40 CFR Part 61, Appendix C, Procedure 2: ``Procedure for Field
Auditing GC Analysis,'' should be performed if audit materials are
available. The information required to document the analysis of the
audit samples has been included on the example data sheets shown in
Figures 18-3 and 18-7. The audit analyses should agree with the
certified audit concentrations within 10 percent. Audit sample results
shall be submitted according to directions provided with the audit
samples.

10.0 Calibration and Standardization.

10.1 Calibration Standards. Obtain calibration gas standards for
each target compound to be analyzed. Commercial cylinder gases
certified by the manufacturer to be accurate to within 1 percent of the
certified label value are preferable, although cylinder gases certified
by the manufacturer to 2 percent accuracy are allowed. Another option
allowed by this method is for the tester to obtain high concentration
certified cylinder gases and then use a dilution system meeting the
requirements of Test Method 205, 40 CFR Part 51, Appendix M to make
multi-level calibration gas standards. Prepare or obtain enough
calibration standards so that there are three different concentrations
of each organic compound expected to be measured in the source sample.
For each organic compound, select those concentrations that bracket the
concentrations expected in the source samples. A calibration standard
may contain more than one organic compound. If samples are collected in
adsorbent tubes and extracted using solvent extraction, prepare or
obtain standards in the same solvent used for the sample extraction
procedure. Verify the stability of all

[[Page 62012]]

standards for the time periods they are used.
10.2 Preparation of Calibration Curves.
10.2.1 Establish proper GC conditions, then flush the sampling
loop for 30 seconds. Allow the sample loop pressure to equilibrate to
atmospheric pressure, and activate the injection valve. Record the
standard concentration, attenuator factor, injection time, chart speed,
retention time, peak area, sample loop temperature, column temperature,
and carrier gas flow rate. Analyze each standard in triplicate.
10.2.2 Repeat this procedure for each standard. Prepare a
graphical plot of concentration (Cs) versus the calibration
area values. Perform a regression analysis, and draw the least square
line.

11.0 Analytical Procedures

11.1 Analysis Development
11.1.1 Selection of GC Parameters
11.1.1.1 Column Choice. Based on the initial contact with plant
personnel concerning the plant process and the anticipated emissions,
choose a column that provides good resolution and rapid analysis time.
The choice of an appropriate column can be aided by a literature
search, contact with manufacturers of GC columns, and discussion with
personnel at the emission source.

Note: Most column manufacturers keep excellent records on their
products. Their technical service departments may be able to
recommend appropriate columns and detector type for separating the
anticipated compounds, and they may be able to provide information
on interferences, optimum operating conditions, and column
limitations. Plants with analytical laboratories may be able to
provide information on their analytical procedures.

11.1.1.2 Preliminary GC Adjustment. Using the standards and column
obtained in Section 11.1.1.1, perform initial tests to determine
appropriate GC conditions that provide good resolution and minimum
analysis time for the compounds of interest.
11.1.1.3 Preparation of Presurvey Samples. If the samples were
collected on an adsorbent, extract the sample as recommended by the
manufacturer for removal of the compounds with a solvent suitable to
the type of GC analysis. Prepare other samples in an appropriate
manner.
11.1.1.4 Presurvey Sample Analysis.
11.1.1.4.1 Before analysis, heat the presurvey sample to the duct
temperature to vaporize any condensed material. Analyze the samples by
the GC procedure, and compare the retention times against those of the
calibration samples that contain the components expected to be in the
stream. If any compounds cannot be identified with certainty by this
procedure, identify them by other means such as GC/mass spectroscopy
(GC/MS) or GC/infrared techniques. A GC/MS system is recommended.
11.1.1.4.2 Use the GC conditions determined by the procedure of
Section 11.1.1.2 for the first injection. Vary the GC parameters during
subsequent injections to determine the optimum settings. Once the
optimum settings have been determined, perform repeat injections of the
sample to determine the retention time of each compound. To inject a
sample, draw sample through the loop at a constant rate (100 ml/min for
30 seconds). Be careful not to pressurize the gas in the loop. Turn off
the pump and allow the gas in the sample loop to come to ambient
pressure. Activate the sample valve, and record injection time, loop
temperature, column temperature, carrier flow rate, chart speed, and
attenuator setting. Calculate the retention time of each peak using the
distance from injection to the peak maximum divided by the chart speed.
Retention times should be repeatable within 0.5 seconds.
11.1.1.4.3 If the concentrations are too high for appropriate
detector response, a smaller sample loop or dilutions may be used for
gas samples, and, for liquid samples, dilution with solvent is
appropriate. Use the standard curves (Section 10.2) to obtain an
estimate of the concentrations.
11.1.1.4.4 Identify all peaks by comparing the known retention
times of compounds expected to be in the retention times of peaks in
the sample. Identify any remaining unidentified peaks which have areas
larger than 5 percent of the total using a GC/MS, or estimation of
possible compounds by their retention times compared to known
compounds, with confirmation by further GC analysis.

12.0 Data Analysis and Calculations

12.1 Nomenclature.

Bws = Water vapor content of the bag sample or stack gas,
proportion by volume.
Cs = Concentration of the organic from the calibration
curve, ppm.
Gv = Gas volume or organic compound injected, ml.
Lv = Liquid volume of organic injected, l.
M = Molecular weight of organic, g/g-mole.
ms = Total mass of compound measured on adsorbent with
spiked train (g).
mu = Total mass of compound measured on adsorbent with
unspiked train (g).
mv = Mass per volume of spiked compound measured
(g/L).
Pi = Barometric or absolute sample loop pressure at time of
sample analysis, mm Hg.
Pm = Absolute pressure of dry gas meter, mm Hg.
Pr = Reference pressure, the barometric pressure or absolute
sample loop pressure recorded during calibration, mm Hg.
Ps = Absolute pressure of syringe before injection, mm Hg.
qc = Flow rate of the calibration gas to be diluted.
qc1 = Flow rate of the calibration gas to be diluted in
stage 1.
qc2 = Flow rate of the calibration gas to be diluted in
stage 2.
qd = Diluent gas flow rate.
qd1 = Flow rate of diluent gas in stage 1.
qd2 = Flow rate of diluent gas in stage 2.
s = Theoretical concentration (ppm) of spiked target compound in the
bag.
S = Theoretical mass of compound spiked onto adsorbent in spiked train
(g).
t = Measured average concentration (ppm) of target compound and source
sample (analysis results subsequent to bag spiking)
Ti = Sample loop temperature at the time of sample analysis,
deg.K.
Tm = Absolute temperature of dry gas meter, deg.K.
Ts = Absolute temperature of syringe before injection,
deg.K.
u = Source sample average concentration (ppm) of target compound in the
bag (analysis results before bag spiking).
Vm = Gas volume indicated by dry gas meter, liters.
vs = volume of stack gas sampled with spiked train (L).
vu = volume of stack gas sampled with unspiked train (L).
X = Mole or volume fraction of the organic in the calibration gas to be
diluted.
Y = Dry gas meter calibration factor, dimensionless.
l = Liquid organic density as determined, g/ml.

24.055 = Ideal gas molar volume at 293 deg.K and 760 mm Hg, liters/g-
mole.

1000 = Conversion factor, ml/liter.
10\6\ = Conversion to ppm.

12.2 Calculate the concentration, Cs, in ppm using the
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.304

[[Page 62013]]

12.3 Calculate the concentration, Cs, in ppm of the
organic in the final gas mixture using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.305

12.4 Calculate each organic standard concentration, Cs,
in ppm using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.306

12.5 Calculate each organic standard concentration, Cs,
in ppm using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.307

12.6 Calculate the concentration, Cc, in ppm, dry
basis, of each organic is the sample using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.308

12.7 Calculate the average fraction recovered (R) of each spiked
target compound using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.309

12.8 Correct all field measurements with the calculated R value
for that compound using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.310

12.9 Determine the mass per volume of spiked compound measured
using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.311

12.10 Calculate the fraction of spiked compound recovered, R,
using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.312

13.0 Method Performance

13.1 Since a potential sample may contain a variety of compounds
from various sources, a specific precision limit for the analysis of
field samples is impractical. Precision in the range of 5 to 10 percent
relative standard deviation (RSD) is typical for gas chromatographic
techniques, but an experienced GC operator with a reliable instrument
can readily achieve 5 percent RSD. For this method, the following
combined GC/operator values are required.
(a) Precision. Triplicate analyses of calibration standards fall
within 5 percent of their mean value.
(b) Accuracy. Analysis results of prepared audit samples are
within 10 percent of preparation values.
(c) Recovery. After developing an appropriate sampling and
analytical system for the pollutants of interest, conduct the procedure
in Section 8.4. Conduct the appropriate recovery study in Section 8.4
at each sampling point where the method is being applied. Submit the
data and results of the recovery procedure with the reporting of
results under Section 8.3.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 Alternative Procedures

16.1 Optional Presurvey and Presurvey Sampling.

[[Page 62014]]

Note: Presurvey screening is optional. Presurvey sampling should
be conducted for sources where the target pollutants are not known
from previous tests and/or process knowledge.

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

[[Page 62015]]

longer to check for desorption of organics from the bag. Follow the
leak-check and sample collection procedures given in Section 8.2.1.
16.1.3.3 Determination of Moisture Content. For combustion or
water-controlled processes, obtain the moisture content from plant
personnel or by measurement during the presurvey. If the source is
below 59 deg.C, measure the wet bulb and dry bulb temperatures, and
calculate the moisture content using a psychrometric chart. At higher
temperatures, use Method 4 to determine the moisture content.
16.1.4 Determination of Static Pressure. Obtain the static
pressure from the plant personnel or measurement. If a type S pitot
tube and an inclined manometer are used, take care to align the pitot
tube 90 deg. from the direction of the flow. Disconnect one of the
tubes to the manometer, and read the static pressure; note whether the
reading is positive or negative.
16.1.5 Collection of Presurvey Samples with Adsorption Tube.
Follow Section 8.2.4 for presurvey sampling.

17.0 References

1. American Society for Testing and Materials. C1 Through C5
Hydrocarbons in the Atmosphere by Gas Chromatography. ASTM D 2820-
72, Part 23. Philadelphia, Pa. 23:950-958. 1973.
2. Corazon, V.V. Methodology for Collecting and Analyzing
Organic Air Pollutants. U.S. Environmental Protection Agency.
Research Triangle Park, N.C. Publication No. EPA-600/2-79-042.
February 1979.
3. Dravnieks, A., B.K. Krotoszynski, J. Whitfield, A. O'Donnell,
and T. Burgwald. Environmental Science and Technology. 5(12):1200-
1222. 1971.
4. Eggertsen, F.T., and F.M. Nelsen. Gas Chromatographic
Analysis of Engine Exhaust and Atmosphere. Analytical Chemistry.
30(6): 1040-1043. 1958.
5. Feairheller, W.R., P.J. Marn, D.H. Harris, and D.L. Harris.
Technical Manual for Process Sampling Strategies for Organic
Materials. U.S. Environmental Protection Agency. Research Triangle
Park, N.C. Publication No. EPA 600/2-76-122. April 1976. 172 p.
6. Federal Register, 39 FR 9319-9323. 1974.
7. Federal Register, 39 FR 32857-32860. 1974.
8. Federal Register, 23069-23072 and 23076-23090. 1976.
9. Federal Register, 46569-46571. 1976.
10. Federal Register, 41771-41776. 1977.
11. Fishbein, L. Chromatography of Environmental Hazards, Volume
II. Elesevier Scientific Publishing Company. New York, N.Y. 1973.
12. Hamersma, J.W., S.L. Reynolds, and R.F. Maddalone. EPA/IERL-
RTP Procedures Manual: Level 1 Environmental Assessment. U.S.
Environmental Protection Agency. Research Triangle Park, N.C.
Publication No. EPA 600/276-160a. June 1976. 130 p.
13. Harris, J.C., M.J. Hayes, P.L. Levins, and D.B. Lindsay.
EPA/IERL-RTP Procedures for Level 2 Sampling and Analysis of Organic
Materials. U.S. Environmental Protection Agency. Research Triangle
Park, N.C. Publication No. EPA 600/7-79-033. February 1979. 154 p.
14. Harris, W.E., H.W. Habgood. Programmed Temperature Gas
Chromatography. John Wiley and Sons, Inc. New York. 1966.
15. Intersociety Committee. Methods of Air Sampling and
Analysis. American Health Association. Washington, D.C. 1972.
16. Jones, P.W., R.D. Grammer, P.E. Strup, and T.B. Stanford.
Environmental Science and Technology. 10:806-810. 1976.
17. McNair Han Bunelli, E.J. Basic Gas Chromatography.
Consolidated Printers. Berkeley. 1969.
18. Nelson, G.O. Controlled Test Atmospheres, Principles and
Techniques. Ann Arbor. Ann Arbor Science Publishers. 1971. 247 p.
19. NIOSH Manual of Analytical Methods, Volumes 1, 2, 3, 4, 5,
6, 7. U.S. Department of Health and Human Services, National
Institute for Occupational Safety and Health. Center for Disease
Control. 4676 Columbia Parkway, Cincinnati, Ohio 45226. April 1977--
August 1981. May be available from the Superintendent of Documents,
Government Printing Office, Washington, D.C. 20402. Stock Number/
Price:

Volume 1--O17-033-00267-3/$13
Volume 2--O17-033-00260-6/$11
Volume 3--O17-033-00261-4/$14
Volume 4--O17-033-00317-3/$7.25
Volume 5--O17-033-00349-1/$10
Volume 6--O17-033-00369-6/$9
Volume 7--O17-033-00396-5/$7

Prices subject to change. Foreign orders add 25 percent.
20. Schuetzle, D., T.J. Prater, and S.R. Ruddell. Sampling and
Analysis of Emissions from Stationary Sources; I. Odor and Total
Hydrocarbons. Journal of the Air Pollution Control Association.
25(9): 925-932. 1975.
21. Snyder, A.D., F.N. Hodgson, M.A. Kemmer and J.R. McKendree.
Utility of Solid Sorbents for Sampling Organic Emissions from
Stationary Sources. U.S. Environmental Protection Agency. Research
Triangle Park, N.C. Publication No. EPA 600/2-76-201. July 1976. 71
p.
22. Tentative Method for Continuous Analysis of Total
Hydrocarbons in the Atmosphere. Intersociety Committee, American
Public Health Association. Washington, D.C. 1972. p. 184-186.
23. Zwerg, G. CRC Handbook of Chromatography, Volumes I and II.
Sherma, Joseph (ed.). CRC Press. Cleveland. 1972.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

I. Name of company-----------------------------------------------------
Date-------------------------------------------------------------------
Address----------------------------------------------------------------
----------------------------------------------------------------------
Contracts--------------------------------------------------------------
Phone------------------------------------------------------------------
Process to be sampled--------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
Duct or vent to be sampled---------------------------------------------
----------------------------------------------------------------------
II. Process description------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
Raw material-----------------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
Products---------------------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------

Operating cycle
Check: Batch ________ Continuous ________ Cyclic ________
Timing of batch or cycle-----------------------------------------------

[[Page 62016]]

Best time to test------------------------------------------------------

III. Sampling site-----------------------------------------------------
A. Description---------------------------------------------------------
Site decription--------------------------------------------------------
Duct shape and size----------------------------------------------------
Material---------------------------------------------------------------
Wall thickness ________ inches
Upstream distance ________ inches ________ diameter
Downstream distance ________ inches ________ diameter
Size of port-----------------------------------------------------------
Size of access area----------------------------------------------------
Hazards ________ Ambient temp. ________ deg.F

B. Properties of gas stream
Temperature ________ deg.C ________ deg.F, Data source ________
Velocity ________, Data source ________
Static pressure ________ inches H2O, Data source ________
Moisture content ________%, Data source ________
Particulate content ________, Data source________

Gaseous components
N2 ________ % Hydrocarbons ________ ppm
O2 ________% ________
CO ________ % ________ ________
CO2 ________ % ________ ________
SO2 ________ % ________ ________

Hydrocarbon components
________ ________ ppm
________ ________ ppm
________ ________ ppm
________ ________ ppm
________ ________ ppm
________ ________ ppm

C. Sampling considerations
Location to set up GC--------------------------------------------------
----------------------------------------------------------------------
Special hazards to be considered---------------------------------------
----------------------------------------------------------------------
Power available at duct------------------------------------------------
Power available for GC-------------------------------------------------
Plant safety requirements----------------------------------------------
----------------------------------------------------------------------
Vehicle traffic rules--------------------------------------------------
----------------------------------------------------------------------
Plant entry requirements-----------------------------------------------
----------------------------------------------------------------------
Security agreements----------------------------------------------------
----------------------------------------------------------------------
Potential problems-----------------------------------------------------
----------------------------------------------------------------------

D. Site diagrams. (Attach additional sheets if required).
Figure 18-1. Preliminary Survey Data Sheet
Components to be analyzed and Expected concentration
----------------------------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
Suggested chromatographic column---------------------------------------
----------------------------------------------------------------------
Column flow rate __ ml/min
Head pressure ________ mm Hg

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

[[Page 62017]]

Compound data:
Compound and Retention time and Attenuation
----------------------------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
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 ( deg.K)................
Average meter pressure, gauge (mm Hg).............
Average atmospheric perssure (mm Hg)..............
Average meter pressure, absolute (mm Hg)..........
Syringe temperature ( deg.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 ( deg.C)......................
Carrier gas flow rate (ml/min)........................
Column temperature:
Initial ( deg.C)......................................
Rate change ( deg.C/min)..............................
Final ( deg.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-------------------------------------
Flowmeter Type---------------------------------------------------------
Method: Bubble meter____ Spirometer____ Wet test meter ____
Readings at laboratory conditions:
Laboratory temperature (Tlab) ____ deg.K
Laboratory barometric pressure (Plab)____ mm Hg
Flow data:

Flowmeter
----------------------------------------------------------------------------------------------------------------
Reading (as marked) Temp. ( deg.K) Pressure (absolute)
----------------------------------------------------------------------------------------------------------------

----------------------------------------------------------------------------------------------------------------

[[Page 62018]]

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 deg.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:

[GRAPHIC] [TIFF OMITTED] TR17OC00.313

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

------------------------------------------------------------------------

Figure 18-4. Flowmeter Calibration
BILLING CODE 6560-50-P

[[Page 62019]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.314

[[Page 62020]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.315

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 ( deg.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

[[Page 62021]]

Calculated concentration (ppm)
GC Operating Conditions:
Sample loop volume (ml)
Sample loop temperature ( deg.C)
Carrier gas flow rate (ml/min)
Column temperature:
Initial ( deg.C)
Program rate ( deg.C/min)
Final ( deg.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

[[Page 62022]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.316

[[Page 62023]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.317

[[Page 62024]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.318

BILLING CODE 6560-50-C

Plant________ Date________ Site________
----------------------------------------------------------------------------------------------------------------
Sample 1 Sample 2 Sample 3
----------------------------------------------------------------------------------------------------------------
Source temperature ( deg.C)..................................... .............. .............. ..............
Barometric pressure (mm Hg)..................................... .............. .............. ..............
Ambient temperature ( deg.C).................................... .............. .............. ..............
Sample flow rate (appr.)........................................ .............. .............. ..............
Bag number...................................................... .............. .............. ..............
Start time...................................................... .............. .............. ..............
Finish time..................................................... .............. .............. ..............
----------------------------------------------------------------------------------------------------------------

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

Plant -------- Date -------- Location --------

m
1. General information:
Source temperature ( deg.C)....................... ................
Probe temperature ( deg.C)........................ ................
Ambient temperature ( deg.C)...................... ................
Atmospheric pressure (mm)......................... ................

[[Page 62025]]

Source pressure ("Hg)............................. ................
Absolute source pressure (mm)..................... ................
Sampling rate (liter/min)......................... ................
Sample loop volume (ml)........................... ................
Sample loop temperature ( deg.C).................. ................
Columnar temperature:
Initial ( deg.C) time (min)................... ................
Program rate ( deg.C/min)..................... ................
Final ( deg.C)/time (min)..................... ................
Carrier gas flow rate (ml/min).................... ................
Detector temperature ( deg.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.________ Time________]
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Components Area Attenuation A x A Factor Conc.__ (ppm)
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
....................... ........................................ ........................................ ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
....................... ........................................ ........................................ ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
....................... ........................................ ........................................ ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
....................... ........................................ ........................................ ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
....................... ........................................ ........................................ ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
....................... ........................................ ........................................ ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
....................... ........................................ ........................................ ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
....................... ........................................ ........................................ ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
....................... ........................................ ........................................ ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
....................... ........................................ ........................................ ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
....................... ........................................ ........................................ ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
....................... ........................................ ........................................ ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
....................... ........................................ ........................................ ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
....................... ........................................ ........................................ ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
....................... ........................................ ........................................ ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

Figure 18-11. Field Analysis Data Sheets
BILLING CODE 6560-50-P

[[Page 62026]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.319

[[Page 62027]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.320

BILLING CODE 6560-50-C

Gaseous Organic Sampling and Analysis Check List
[Respond with initials or number as appropriate]

Date

1. Presurvey data:
A. Grab sample collected........................ {time} ______
B. Grab sample analyzed for composition..... {time} ______
Method GC................................... {time} ______
GC/MS................................... {time} ______
Other................................... {time} ______
C. GC-FID analysis performed.................... {time} ______
2. Laboratory calibration data:
A. Calibration curves prepared.................. {time} ______
Number of components........................ {time} ______
Number of concentrations/component (3 {time} ______
required).
B. Audit samples (optional):
Analysis completed.............................. {time} ______
Verified for concentration...................... {time} ______
OK obtained for field work...................... {time} ______
3. Sampling procedures:
A. Method:
Bag sample.................................. {time} ______
Direct interface............................ {time} ______
Dilution interface.......................... {time} ______
B. Number of samples collected.................. {time} ______
4. Field Analysis:
A. Total hydrocarbon analysis performed......... {time} ______

[[Page 62028]]

B. Calibration curve prepared................... {time} ______
Number of components........................ {time} ______
Number of concentrations per component (3 {time} ______
required).

Gaseous Organic Sampling and Analysis Data
Plant------------------------------------------------------------------
Date-------------------------------------------------------------------
Location---------------------------------------------------------------

----------------------------------------------------------------------------------------------------------------
Source sample 1 Source sample 2 Source sample 3
---------------------------------------------------------------------------------------------------------------
1. General information:
Source temperature ( deg.C)....... .................................. ..................................
Probe temperature ( deg.C)........ .................................. ..................................
Ambient temperature ( deg.C)...... .................................. ..................................
Atmospheric pressure (mm Hg)...... .................................. ..................................
Source pressure (mm Hg)........... .................................. ..................................
Sampling rate (ml/min)............ .................................. ..................................
Sample loop volume (ml)........... .................................. ..................................
Sample loop temperature ( deg.C).. .................................. ..................................
Sample collection time (24-hr .................................. ..................................
basis).
Column temperature:
Initial ( deg.C).............. .................................. ..................................
Program rate ( deg.C/min)..... .................................. ..................................
Final ( deg.C)................ .................................. ..................................
Carrier gas flow rate (ml/min).... .................................. ..................................
Detector temperature ( deg.C)..... .................................. ..................................
Chart speed (cm/min).............. .................................. ..................................
Dilution gas flow rate (ml/min)... .................................. ..................................
Diluent gas used (symbol)......... .................................. ..................................
Dilution ratio.................... .................................. ..................................
Performed by: (signature):________________________ Date:________________________
----------------------------------------------------------------------------------------------------------------

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),
including:
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 by an applicable subpart of the
regulations, this method is applicable for the determination of (a) PM,
SO2, and NOX emission rates; (b) sulfur removal
efficiencies of fuel pretreatment and SO2 control devices;
and (c) overall reduction of potential SO2 emissions.

2.0 Summary of Method

2.1 Emission Rates. Oxygen (O2) or carbon dioxide
(CO2) concentrations and appropriate F factors (ratios of
combustion gas volumes to heat inputs) are used to calculate pollutant
emission rates from pollutant concentrations.
2.2 Sulfur Reduction Efficiency and SO2 Removal
Efficiency. An overall SO2 emission reduction efficiency is
computed from the efficiency of fuel pretreatment systems, where
applicable, and the efficiency of SO2 control devices.
2.2.1 The sulfur removal efficiency of a fuel pretreatment system
is determined by fuel sampling and analysis of the sulfur and heat
contents of the fuel before and after the pretreatment system.
2.2.2 The SO2 removal efficiency of a control device is
determined by measuring the SO2 rates before and after the
control device.
2.2.2.1 The inlet rates to SO2 control systems (or,
when SO2 control systems are not used, SO2
emission rates to the atmosphere) are determined by fuel sampling and
analysis.

[[Page 62029]]

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety [Reserved]

6.0 Equipment and Supplies [Reserved]

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection, Preservation, Storage, and Transport [Reserved]

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedures [Reserved]

12.0 Data Analysis and Calculations

12.1 Nomenclature

Bwa = Moisture fraction of ambient air, percent.
Bws = Moisture fraction of effluent gas, percent.
%C = Concentration of carbon from an ultimate analysis of fuel, weight
percent.
Cd = Pollutant concentration, dry basis, ng/scm (lb/scf)
%CO2d,%CO2w = Concentration of carbon dioxide on
a dry and wet basis, respectively, percent.
Cw = Pollutant concentration, wet basis, ng/scm (lb/scf).
D = Number of sampling periods during the performance test period.
E = Pollutant emission rate, ng/J (lb/million Btu).
Ea = Average pollutant rate for the specified performance
test period, ng/J (lb/million Btu).
Eao, Eai = Average pollutant rate of the control
device, outlet and inlet, respectively, for the performance test
period, ng/J (lb/million Btu).
Ebi = Pollutant rate from the steam generating unit, ng/J
(lb/million Btu)
Ebo = Pollutant emission rate from the steam generating
unit, ng/J (lb/million Btu).
Eci = Pollutant rate in combined effluent, ng/J (lb/million
Btu).
Eco = Pollutant emission rate in combined effluent, ng/J
(lb/million Btu).
Ed = Average pollutant rate for each sampling period (e.g.,
24-hr Method 6B sample or 24-hr fuel sample) or for each fuel lot
(e.g., amount of fuel bunkered), ng/J (lb/million Btu).
Edi = Average inlet SO2 rate for each sampling
period d, ng/J (lb/million Btu)
Eg = Pollutant rate from gas turbine, ng/J (lb/million Btu).
Ega = Daily geometric average pollutant rate, ng/J (lbs/
million Btu) or ppm corrected to 7 percent O2.
Ejo,Eji = Matched pair hourly arithmetic average
pollutant rate, outlet and inlet, respectively, ng/J (lb/million Btu)
or ppm corrected to 7 percent O2.
Eh = Hourly average pollutant, ng/J (lb/million Btu).
Ehj = Hourly arithmetic average pollutant rate for hour
``j,'' ng/J (lb/million Btu) or ppm corrected to 7 percent
O2.
EXP = Natural logarithmic base (2.718) raised to the value enclosed by
brackets.
Fd, Fw, Fc = Volumes of combustion
components per unit of heat content, scm/J (scf/million Btu).
GCV = Gross calorific value of the fuel consistent with the ultimate
analysis, kJ/kg (Btu/lb).
GCVp, GCVr = Gross calorific value for the
product and raw fuel lots, respectively, dry basis, kJ/kg (Btu/lb).
%H = Concentration of hydrogen from an ultimate analysis of fuel,
weight percent.
H = Total number of operating hours for which pollutant rates are
determined in the performance test period.
Hb = Heat input rate to the steam generating unit from fuels
fired in the steam generating unit, J/hr (million Btu/hr).
Hg = Heat input rate to gas turbine from all fuels fired in
the gas turbine, J/hr (million Btu/hr).
%H2O = Concentration of water from an ultimate analysis of
fuel, weight percent.
Hr = Total numbers of hours in the performance test period
(e.g., 720 hours for 30-day performance test period).
K = Conversion factor, 10-\5\ (kJ/J)/(%) [106
Btu/million Btu].
Kc = (9.57 scm/kg)/% [(1.53 scf/lb)/%].
Kcc = (2.0 scm/kg)/% [(0.321 scf/lb)/%].
Khd = (22.7 scm/kg)/% [(3.64 scf/lb)/%].
Khw = (34.74 scm/kg)/% [(5.57 scf/lb)/%].
Kn = (0.86 scm/kg)/% [(0.14 scf/lb)/%].
Ko = (2.85 scm/kg)/% [(0.46 scf/lb)/%].
Ks = (3.54 scm/kg)/% [(0.57 scf/lb)/%].
Kw = (1.30 scm/kg)/% [(0.21 scf/lb)/%].
ln = Natural log of indicated value.
Lp,Lr = Weight of the product and raw fuel lots,
respectively, metric ton (ton).
%N = Concentration of nitrogen from an ultimate analysis of fuel,
weight percent.
N = Number of fuel lots during the averaging period.
n = Number of fuels being burned in combination.
nd = Number of operating hours of the affected facility
within the performance test period for each Ed determined.
nt = Total number of hourly averages for which paired inlet
and outlet pollutant rates are available within the 24-hr midnight to
midnight daily period.
%O = Concentration of oxygen from an ultimate analysis of fuel, weight
percent.
%O2d, %O2w = Concentration of oxygen on a dry and
wet basis, respectively, percent.
Ps = Potential SO2 emissions, percent.
%Rf = SO2 removal efficiency from fuel
pretreatment, percent.
%Rg = SO2 removal efficiency of the control
device, percent.
%Rga = Daily geometric average percent reduction.
%Ro = Overall SO2 reduction, percent.
%S = Sulfur content of as-fired fuel lot, dry basis, weight percent.
Se = Standard deviation of the hourly average pollutant
rates for each performance test period, ng/J (lb/million Btu).
%Sf = Concentration of sulfur from an ultimate analysis of
fuel, weight percent.
Si = Standard deviation of the hourly average inlet
pollutant rates for each performance test period, ng/J (lb/million
Btu).
So = Standard deviation of the hourly average emission rates
for each performance test period, ng/J (lb/million Btu).
%Sp, %Sr = Sulfur content of the product and raw
fuel lots respectively, dry basis, weight percent.
t0.95 = Values shown in Table 19-3 for the indicated number
of data points n.
Xk = Fraction of total heat input from each type of fuel k.

12.2 Emission Rates of PM, SO2, and NOx.
Select from the following sections the applicable procedure to compute
the PM, SO2, or NOx emission rate (E) in ng/J
(lb/million Btu). The pollutant concentration must be in ng/scm (lb/
scf) and the F factor must be in scm/J (scf/million Btu). If the
pollutant concentration (C) is not in the appropriate units, use Table
19-1 in Section 17.0 to make the proper conversion. An F factor is the
ratio of the gas volume of the products of combustion to the heat
content of the fuel. The dry F factor (Fd) includes all
components of combustion less water, the wet F factor (Fw)
includes all components of combustion, and the carbon F factor
(Fc) includes only carbon dioxide.

Note: Since Fw factors include water resulting only
from the combustion of

[[Page 62030]]

hydrogen in the fuel, the procedures using Fw factors are
not applicable for computing E from steam generating units with wet
scrubbers or with other processes that add water (e.g., steam
injection).

12.2.1 Oxygen-Based F Factor, Dry Basis. When measurements are on
a dry basis for both O (%O2d) and pollutant (Cd)
concentrations, use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.321

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:
[GRAPHIC] [TIFF OMITTED] TR17OC00.322

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:
[GRAPHIC] [TIFF OMITTED] TR17OC00.323

12.2.3 Oxygen-Based F Factor, Dry/Wet Basis.
12.2.3.1 When the pollutant concentration is measured on a wet
basis (Cw) and O2 concentration is measured on a
dry basis (%O2d), use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.324

12.2.3.2 When the pollutant concentration is measured on a dry
basis (Cd) and the O2 concentration is measured
on a wet basis (%O2w), use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.325

12.2.4 Carbon Dioxide-Based F Factor, Dry Basis. When measurements
are on a dry basis for both CO2 (%CO2d) and
pollutant (Cd) concentrations, use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.326

12.2.5 Carbon Dioxide-Based F Factor, Wet Basis. When measurements
are on a wet basis for both CO2 (%CO2w) and
pollutant (Cw) concentrations, use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.327

12.2.6 Carbon Dioxide-Based F Factor, Dry/Wet Basis.
12.2.6.1 When the pollutant concentration is measured on a wet
basis (Cw) and CO2 concentration is measured on a
dry basis (%CO2d), use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.328

12.2.6.2 When the pollutant concentration is measured on a dry
basis (Cd) and CO2 concentration is measured on a
wet basis (%CO2w), use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.329

12.2.7 Direct-Fired Reheat Fuel Burning. The effect of direct-
fired reheat fuel burning (for the purpose of raising the temperature
of the exhaust effluent from wet scrubbers to above the moisture dew-
point) on emission rates will be less than 1.0 percent and, therefore,
may be ignored.
12.2.8 Combined Cycle-Gas Turbine Systems. For gas turbine-steam
generator combined cycle systems, determine the emissions from the
steam generating unit or the percent reduction in potential
SO2 emissions as follows:
12.2.8.1 Compute the emission rate from the steam generating unit
using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.330

12.2.8.1.1 Use the test methods and procedures section of 40 CFR
Part 60, Subpart GG to obtain Eco and Eg. Do not
use Fw factors for determining Eg or
Eco. If an SO2 control device is used, measure
Eco after the control device.
12.2.8.1.2 Suitable methods shall be used to determine the heat
input rates to the steam generating units (Hb) and the gas
turbine (Hg).
12.2.8.2 If a control device is used, compute the percent of
potential SO2 emissions (Ps) using the following
equations:
[GRAPHIC] [TIFF OMITTED] TR17OC00.331

[GRAPHIC] [TIFF OMITTED] TR17OC00.332

[[Page 62031]]

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:
[GRAPHIC] [TIFF OMITTED] TR17OC00.333

[GRAPHIC] [TIFF OMITTED] TR17OC00.334

[GRAPHIC] [TIFF OMITTED] TR17OC00.335

Note: Omit the %H2O term in the equations for
Fw if %H and %O include the unavailable hydrogen and
oxygen in the form of H2O.)

12.3.2.2 Use applicable sampling procedures in Section 12.5.2.1 or
12.5.2.2 to obtain samples for analyses.
12.3.2.3 Use ASTM D 3176-74 or 89 (all cited ASTM standards are
incorporated by reference--see Sec. 60.17) for ultimate analysis of the
fuel.
12.3.2.4 Use applicable methods in Section 12.5.2.1 or 12.5.2.2 to
determine the heat content of solid or liquid fuels. For gaseous fuels,
use ASTM D 1826-77 or 94 (incorporated by reference--see Sec. 60.17) to
determine the heat content.
12.3.3 F Factors for Combination of Fuels. If combinations of
fuels are burned, use the following equations, as applicable unless
otherwise specified in an applicable subpart:
[GRAPHIC] [TIFF OMITTED] TR17OC00.336

[GRAPHIC] [TIFF OMITTED] TR17OC00.337

[GRAPHIC] [TIFF OMITTED] TR17OC00.338

12.4 Determination of Average Pollutant Rates.
12.4.1 Average Pollutant Rates from Hourly Values. When hourly
average pollutant rates (Eh), inlet or outlet, are obtained
(e.g., CEMS values), compute the average pollutant rate (Ea)
for the performance test period (e.g., 30 days) specified in the
applicable regulation using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.339

12.4.2 Average Pollutant Rates from Other than Hourly Averages.
When pollutant rates are determined from measured values representing
longer than 1-hour periods (e.g., daily fuel sampling and analyses or
Method 6B values), or when pollutant rates are determined from
combinations of 1-hour and longer than 1-hour periods (e.g., CEMS and
Method 6B values), compute the average pollutant rate (Ea)
for the performance test period (e.g., 30 days) specified in the
applicable regulation using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.340

12.4.3 Daily Geometric Average Pollutant Rates from Hourly Values.
The geometric average pollutant rate (Ega) is computed using
the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.341

12.5 Determination of Overall Reduction in Potential Sulfur
Dioxide Emission.
12.5.1 Overall Percent Reduction. Compute the overall percent
SO2 reduction (%Ro) using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.342

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:
[GRAPHIC] [TIFF OMITTED] TR17OC00.343

Note: In calculating %Rf, include %S and GCV values
for all fuel lots that are not pretreated and are used during the
averaging period.

12.5.2.1 Solid Fossil (Including Waste) Fuel/Sampling and
Analysis.

[[Page 62032]]

Note: For the purposes of this method, raw fuel (coal or oil) is
the fuel delivered to the desulfurization (pretreatment) facility.
For oil, the input oil to the oil desulfurization process (e.g.,
hydrotreatment) is considered to be the raw fuel.

12.5.2.1.1 Sample Increment Collection. Use ASTM D 2234-76, 96,
97a, or 98 (incorporated by reference--see Sec. 60.17), Type I,
Conditions A, B, or C, and systematic spacing. As used in this method,
systematic spacing is intended to include evenly spaced increments in
time or increments based on equal weights of coal passing the
collection area. As a minimum, determine the number and weight of
increments required per gross sample representing each coal lot
according to Table 2 or Paragraph 7.1.5.2 of ASTM D 2234. Collect one
gross sample for each lot of raw coal and one gross sample for each lot
of product coal.
12.5.2.1.2 ASTM Lot Size. For the purpose of Section 12.5.2 (fuel
pretreatment), the lot size of product coal is the weight of product
coal from one type of raw coal. The lot size of raw coal is the weight
of raw coal used to produce one lot of product coal. Typically, the lot
size is the weight of coal processed in a 1-day (24-hour) period. If
more than one type of coal is treated and produced in 1 day, then gross
samples must be collected and analyzed for each type of coal. A coal
lot size equaling the 90-day quarterly fuel quantity for a steam
generating unit may be used if representative sampling can be conducted
for each raw coal and product coal.

Note: Alternative definitions of lot sizes may be used, subject
to prior approval of the Administrator.

12.5.2.1.3 Gross Sample Analysis. Use ASTM D 2013-72 or 86 to
prepare the sample, ASTM D 3177-75 or 89 or ASTM D 4239-85, 94, or 97
to determine sulfur content (%S), ASTM D 3173-73 or 87 to determine
moisture content, and ASTM D 2015-77 (Reapproved 1978) or 96, D 3286-85
or 96, or D 5865-98 to determine gross calorific value (GCV) (all
standards cited are incorporated by reference--see Sec. 60.17 for
acceptable versions of the standards) on a dry basis for each gross
sample.
12.5.2.2 Liquid Fossil Fuel-Sampling and Analysis. See Note under
Section 12.5.2.1.
12.5.2.2.1 Sample Collection. Follow the procedures for continuous
sampling in ASTM D 270 or D 4177-95 (incorporated by reference--see
Sec. 60.17) for each gross sample from each fuel lot.
12.5.2.2.2 Lot Size. For the purpose of Section 12.5.2 (fuel
pretreatment), the lot size of a product oil is the weight of product
oil from one pretreatment facility and intended as one shipment (ship
load, barge load, etc.). The lot size of raw oil is the weight of each
crude liquid fuel type used to produce a lot of product oil.

Note: Alternative definitions of lot sizes may be used, subject
to prior approval of the Administrator.

12.5.2.2.3 Sample Analysis. Use ASTM D 129-64, 78, or 95, ASTM D
1552-83 or 95, or ASTM D 4057-81 or 95 to determine the sulfur content
(%S) and ASTM D 240-76 or 92 (all standards cited are incorporated by
reference--see Sec. 60.17) to determine the GCV of each gross sample.
These values may be assumed to be on a dry basis. The owner or operator
of an affected facility may elect to determine the GCV by sampling the
oil combusted on the first steam generating unit operating day of each
calendar month and then using the lowest GCV value of the three GCV
values per quarter for the GCV of all oil combusted in that calendar
quarter.
12.5.2.3 Use appropriate procedures, subject to the approval of
the Administrator, to determine the fraction of total mass input
derived from each type of fuel.
12.5.3 Control Device Removal Efficiency. Compute the percent
removal efficiency (%Rg) of the control device using the
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.344

12.5.3.1 Use continuous emission monitoring systems or test
methods, as appropriate, to determine the outlet SO2 rates
and, if appropriate, the inlet SO2 rates. The rates may be
determined as hourly (Eh) or other sampling period averages
(Ed). Then, compute the average pollutant rates for the
performance test period (Eao and Eai) using the
procedures in Section 12.4.
12.5.3.2 As an alternative, as-fired fuel sampling and analysis
may be used to determine inlet SO2 rates as follows:
12.5.3.2.1 Compute the average inlet SO2 rate
(Edi) for each sampling period using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.345

Where:
[GRAPHIC] [TIFF OMITTED] TR17OC00.346

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

[[Page 62033]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.347

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:
[GRAPHIC] [TIFF OMITTED] TR17OC00.348

Where:
[GRAPHIC] [TIFF OMITTED] TR17OC00.349

After calculating Edi, use the procedures in Section
12.4.2 to determine the average SO2 emission rate to the
atmosphere for the performance test period (Eao).
12.7 Determination of Compliance When Minimum Data Requirement Is
Not Met.
12.7.1 Adjusted Emission Rates and Control Device Removal
Efficiency. When the minimum data requirement is not met, the
Administrator may use the following adjusted emission rates or control
device removal efficiencies to determine compliance with the applicable
standards.
12.7.1.1 Emission Rate. Compliance with the emission rate standard
may be determined by using the lower confidence limit of the emission
rate (Eao*) as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.350

12.7.1.2 Control Device Removal Efficiency. Compliance with the
overall emission reduction (%Ro) may be determined by using
the lower confidence limit of the emission rate (Eao*) and
the upper confidence limit of the inlet pollutant rate
(Eai*) in calculating the control device removal efficiency
(%Rg) as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.351

[GRAPHIC] [TIFF OMITTED] TR17OC00.352

12.7.2 Standard Deviation of Hourly Average Pollutant Rates.
Compute the standard deviation (Se) of the hourly average
pollutant rates using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.353

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......................... 10\9\
mg/scm.................................. ng/scm......................... 10\6\
lb/scf.................................. ng/scm......................... 1.602 x 10\13\
ppm SO2................................. ng/scm......................... 2.66 x 10\6\
ppm NOx................................. ng/scm......................... 1.912 x 10\6\
ppm SO2................................. lb/scf......................... 1.660 x 10-\7\
ppm NOx................................. lb/scf......................... 1.194 x 10-7
----------------------------------------------------------------------------------------------------------------

[[Page 62034]]

Table 19-2.--F Factors for Various Fuels\1\
--------------------------------------------------------------------------------------------------------------------------------------------------------
Fd Fw Fc
Fuel Type -----------------------------------------------------------------------------------------------
dscm/J dscf/10\6\ Btu wscm/J wscf/10\6\ Btu scm/J scf/10\6\ Btu
--------------------------------------------------------------------------------------------------------------------------------------------------------
Coal:
Anthracite 2........................................ 2.71 x 10-7 10,100 2.83 x 10-7 10,540 0.530 x 10-7 1,970
Bituminus 2......................................... 2.63 x 10-7 9,780 2.86 x 10-7 10,640 0.484 x 10-7 1,800
Lignite............................................. 2.65 x 10-7 9,860 3.21 x 10-7 11,950 0.513 x 10-7 1,910
Oil \3\............................................. 2.47 x 10-7 9,190 2.77 x 10-7 10,320 0.383 x 10-7 1,420
Gas:....................................................
Natural............................................. 2.34 x 10-7 8,710 2.85 x 10-7 10,610 0.287 x 10-7 1,040
Propane............................................. 2.34 x 10-7 8,710 2.74 x 10-7 10,200 0.321 x 10-7 1,190
Butane.............................................. 2.34 x 10-7 8,710 2.79 x 10-7 10,390 0.337 x 10-7 1,250
Wood.................................................... 2.48 x 10-7 9,240 .............. .............. 0.492 x 10-7 1,830
Wood Bark............................................... 2.58 x 10-7 9,600 .............. .............. 0.516 x 10-7 1,920
Municipal............................................... 2.57 x 10-7 9,570 .............. .............. 0.488 x 10-7 1,820
Solid Waste............................................. .............. .............. .............. .............. .............. ..............
--------------------------------------------------------------------------------------------------------------------------------------------------------
\1\ Determined at standard conditions: 20 deg.C (68 deg.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*
----------------------------------------------------------------------------------------------------------------
n\1\ t0.95 n\1\ t0.95 n\1\ 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
----------------------------------------------------------------------------------------------------------------
\1\The values of this table are corrected for n-1 degrees of freedom. Use n equal to the number (H) of hourly
average data points.

* * * * *

Method 21--Determination of Volatile Organic Compound Leaks

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Volatile Organic Compounds (VOC).......... No CAS number assigned.
------------------------------------------------------------------------

1.2 Scope. This method is applicable for the determination of VOC
leaks from process equipment. These sources include, but are not
limited to, valves, flanges and other connections, pumps and
compressors, pressure relief devices, process drains, open-ended
valves, pump and compressor seal system degassing vents, accumulator
vessel vents, agitator seals, and access door seals.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A portable instrument is used to detect VOC leaks from
individual sources. The instrument detector type is not specified, but
it must meet the specifications and performance criteria contained in
Section 6.0. A leak definition concentration based on a reference
compound is specified in each applicable regulation. This method is
intended to locate and classify leaks only, and is not to be used as a
direct measure of mass emission rate from individual sources.

3.0 Definitions

3.1 Calibration gas means the VOC compound used to adjust the
instrument meter reading to a known value. The calibration gas is
usually the reference compound at a known concentration approximately
equal to the leak definition concentration.
3.2 Calibration precision means the degree of agreement between
measurements of the same known value, expressed as the relative
percentage of the average difference between the meter readings and the
known concentration to the known concentration.
3.3 Leak definition concentration means the local VOC
concentration at the surface of a leak source that indicates that a VOC
emission (leak) is present. The leak definition is an instrument meter
reading based on a reference compound.
3.4 No detectable emission means a local VOC concentration at the
surface of a leak source, adjusted for local VOC ambient concentration,
that is less than 2.5 percent of the specified leak definition
concentration. that indicates that a VOC emission (leak) is not
present.
3.5 Reference compound means the VOC species selected as the
instrument calibration basis for specification of the leak definition
concentration. (For example, if a leak definition concentration is
10,000 ppm as methane, then any source emission that results in a local
concentration that yields a meter reading of 10,000 on an instrument
meter calibrated with methane would be classified as a leak. In this
example, the leak definition concentration is 10,000 ppm and the
reference compound is methane.)
3.6 Response factor means the ratio of the known concentration of
a VOC compound to the observed meter reading when measured using an
instrument calibrated with the reference compound specified in the
applicable regulation.
3.7 Response time means the time interval from a step change in
VOC concentration at the input of the sampling system to the time at
which 90 percent of the corresponding final value is reached as
displayed on the instrument readout meter.

[[Page 62035]]

4.0 Interferences. [Reserved]

5.0 Safety

5.1 Disclaimer. This method may involve hazardous materials,
operations, and equipment. This test method may not address all of the
safety problems associated with its use. It is the responsibility of
the user of this test method to establish appropriate safety and health
practices and determine the applicability of regulatory limitations
prior to performing this test method.
5.2 Hazardous Pollutants. Several of the compounds, leaks of which
may be determined by this method, may be irritating or corrosive to
tissues (e.g., heptane) or may be toxic (e.g., benzene, methyl
alcohol). Nearly all are fire hazards. Compounds in emissions should be
determined through familiarity with the source. Appropriate precautions
can be found in reference documents, such as reference No. 4 in Section
16.0.

6.0 Equipment and Supplies

A VOC monitoring instrument meeting the following specifications is
required:
6.1 The VOC instrument detector shall respond to the compounds
being processed. Detector types that may meet this requirement include,
but are not limited to, catalytic oxidation, flame ionization, infrared
absorption, and photoionization.
6.2 The instrument shall be capable of measuring the leak
definition concentration specified in the regulation.
6.3 The scale of the instrument meter shall be readable to
2.5 percent of the specified leak definition concentration.
6.4 The instrument shall be equipped with an electrically driven
pump to ensure that a sample is provided to the detector at a constant
flow rate. The nominal sample flow rate, as measured at the sample
probe tip, shall be 0.10 to 3.0 l/min (0.004 to 0.1 ft\3\/min) when the
probe is fitted with a glass wool plug or filter that may be used to
prevent plugging of the instrument.
6.5 The instrument shall be equipped with a probe or probe
extension or sampling not to exceed 6.4 mm (\1/4\ in) in outside
diameter, with a single end opening for admission of sample.
6.6 The instrument shall be intrinsically safe for operation in
explosive atmospheres as defined by the National Electrical Code by the
National Fire Prevention Association or other applicable regulatory
code for operation in any explosive atmospheres that may be encountered
in its use. The instrument shall, at a minimum, be intrinsically safe
for Class 1, Division 1 conditions, and/or Class 2, Division 1
conditions, as appropriate, as defined by the example code. The
instrument shall not be operated with any safety device, such as an
exhaust flame arrestor, removed.

7.0 Reagents and Standards

7.1 Two gas mixtures are required for instrument calibration and
performance evaluation:
7.1.1 Zero Gas. Air, less than 10 parts per million by volume
(ppmv) VOC.
7.1.2 Calibration Gas. For each organic species that is to be
measured during individual source surveys, obtain or prepare a known
standard in air at a concentration approximately equal to the
applicable leak definition specified in the regulation.
7.2 Cylinder Gases. If cylinder calibration gas mixtures are used,
they must be analyzed and certified by the manufacturer to be within 2
percent accuracy, and a shelf life must be specified. Cylinder
standards must be either reanalyzed or replaced at the end of the
specified shelf life.
7.3 Prepared Gases. Calibration gases may be prepared by the user
according to any accepted gaseous preparation procedure that will yield
a mixture accurate to within 2 percent. Prepared standards must be
replaced each day of use unless it is demonstrated that degradation
does not occur during storage.
7.4 Mixtures with non-Reference Compound Gases. Calibrations may
be performed using a compound other than the reference compound. In
this case, a conversion factor must be determined for the alternative
compound such that the resulting meter readings during source surveys
can be converted to reference compound results.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Instrument Performance Evaluation. Assemble and start up the
instrument according to the manufacturer's instructions for recommended
warmup period and preliminary adjustments.
8.1.1 Response Factor. A response factor must be determined for
each compound that is to be measured, either by testing or from
reference sources. The response factor tests are required before
placing the analyzer into service, but do not have to be repeated at
subsequent intervals.
8.1.1.1 Calibrate the instrument with the reference compound as
specified in the applicable regulation. Introduce the calibration gas
mixture to the analyzer and record the observed meter reading.
Introduce zero gas until a stable reading is obtained. Make a total of
three measurements by alternating between the calibration gas and zero
gas. Calculate the response factor for each repetition and the average
response factor.
8.1.1.2 The instrument response factors for each of the individual
VOC to be measured shall be less than 10 unless otherwise specified in
the applicable regulation. When no instrument is available that meets
this specification when calibrated with the reference VOC specified in
the applicable regulation, the available instrument may be calibrated
with one of the VOC to be measured, or any other VOC, so long as the
instrument then has a response factor of less than 10 for each of the
individual VOC to be measured.
8.1.1.3 Alternatively, if response factors have been published for
the compounds of interest for the instrument or detector type, the
response factor determination is not required, and existing results may
be referenced. Examples of published response factors for flame
ionization and catalytic oxidation detectors are included in References
1-3 of Section 17.0.
8.1.2 Calibration Precision. The calibration precision test must
be completed prior to placing the analyzer into service and at
subsequent 3-month intervals or at the next use, whichever is later.
8.1.2.1 Make a total of three measurements by alternately using
zero gas and the specified calibration gas. Record the meter readings.
Calculate the average algebraic difference between the meter readings
and the known value. Divide this average difference by the known
calibration value and multiply by 100 to express the resulting
calibration precision as a percentage.
8.1.2.2 The calibration precision shall be equal to or less than
10 percent of the calibration gas value.
8.1.3 Response Time. The response time test is required before
placing the instrument into service. If a modification to the sample
pumping system or flow configuration is made that would change the
response time, a new test is required before further use.
8.1.3.1 Introduce zero gas into the instrument sample probe. When
the meter reading has stabilized, switch quickly to the specified
calibration gas. After switching, measure the time required to attain
90 percent of the final stable reading. Perform this test sequence
three times and record the

[[Page 62036]]

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

9.0 Quality Control

[[Page 62037]]

10.0 Calibration and Standardization

10.1 Calibrate the VOC monitoring instrument as follows. After the
appropriate warmup period and zero internal calibration procedure,
introduce the calibration gas into the instrument sample probe. Adjust
the instrument meter readout to correspond to the calibration gas
value.

Note: If the meter readout cannot be adjusted to the proper
value, a malfunction of the analyzer is indicated and corrective
actions are necessary before use.

11.0 Analytical Procedures. [Reserved]

12.0 Data Analyses and Calculations. [Reserved]

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. Dubose, D.A., and G.E. Harris. Response Factors of VOC
Analyzers at a Meter Reading of 10,000 ppmv for Selected Organic
Compounds. U.S. Environmental Protection Agency, Research Triangle
Park, NC. Publication No. EPA 600/2-81051. September 1981.
2. Brown, G.E., et al. Response Factors of VOC Analyzers
Calibrated with Methane for Selected Organic Compounds. U.S.
Environmental Protection Agency, Research Triangle Park, NC.
Publication No. EPA 600/2-81-022. May 1981.
3. DuBose, D.A. et al. Response of Portable VOC Analyzers to
Chemical Mixtures. U.S. Environmental Protection Agency, Research
Triangle Park, NC. Publication No. EPA 600/2-81-110. September 1981.
4. Handbook of Hazardous Materials: Fire, Safety, Health.
Alliance of American Insurers. Schaumberg, IL. 1983.

17.0 Tables, Diagrams, Flowcharts, and Validation Data. [Reserved]

Method 22--Visual Determination of Fugitive Emissions From Material
Sources and Smoke Emissions From Flares

Note: This method is not inclusive with respect to observer
certification. Some material is incorporated by reference from
Method 9.

1.0 Scope and Application

This method is applicable for the determination of the frequency of
fugitive emissions from stationary sources, only as specified in an
applicable subpart of the regulations. This method also is applicable
for the determination of the frequency of visible smoke emissions from
flares.

2.0 Summary of Method

2.1 Fugitive emissions produced during material processing,
handling, and transfer operations or smoke emissions from flares are
visually determined by an observer without the aid of instruments.
2.2 This method is used also to determine visible smoke emissions
from flares used for combustion of waste process materials.
2.3 This method determines the amount of time that visible
emissions occur during the observation period (i.e., the accumulated
emission time). This method does not require that the opacity of
emissions be determined. Since this procedure requires only the
determination of whether visible emissions occur and does not require
the determination of opacity levels, observer certification according
to the procedures of Method 9 is not required. However, it is necessary
that the observer is knowledgeable with respect to the general
procedures for determining the presence of visible emissions. At a
minimum, the observer must be trained and knowledgeable regarding the
effects of background contrast, ambient lighting, observer position
relative to lighting, wind, and the presence of uncombined water
(condensing water vapor) on the visibility of emissions. This training
is to be obtained from written materials found in References 1 and 2 or
from the lecture portion of the Method 9 certification course.

3.0 Definitions

3.1 Emission frequency means the percentage of time that emissions
are visible during the observation period.
3.2 Emission time means the accumulated amount of time that
emissions are visible during the observation period.
3.3 Fugitive emissions means emissions generated by an affected
facility which is not collected by a capture system and is released to
the atmosphere. This includes emissions that (1) escape capture by
process equipment exhaust hoods; (2) are emitted during material
transfer; (3) are emitted from buildings housing material processing or
handling equipment; or (4) are emitted directly from process equipment.
3.4 Observation period means the accumulated time period during
which observations are conducted, not to be less than the period
specified in the applicable regulation.
3.5 Smoke emissions means a pollutant generated by combustion in a
flare and occurring immediately downstream of the flame. Smoke
occurring within the flame, but not downstream of the flame, is not
considered a smoke emission.

4.0 Interferences

4.1 Occasionally, fugitive emissions from sources other than the
affected facility (e.g., road dust) may prevent a clear view of the
affected facility. This may particularly be a problem during periods of
high wind. If the view of the potential emission points is obscured to
such a degree that the observer questions the validity of continuing
observations, then the observations shall be terminated, and the
observer shall clearly note this fact on the data form.

5.0 Safety

6.0 Equipment

6.1 Stopwatches (two). Accumulative type with unit divisions of at
least 0.5 seconds.
6.2 Light Meter. Light meter capable of measuring illuminance in
the 50 to 200 lux range, required for indoor observations only.

7.0 Reagents and Supplies. [Reserved]

8.0 Sample Collection, Preservation, Storage, and Transfer. [Reserved]

9.0 Quality Control. [Reserved]

10.0 Calibration and Standardization. [Reserved]

11.0 Analytical Procedure

11.1 Selection of Observation Location. Survey the affected
facility, or the building or structure housing the process to be
observed, and determine the locations of potential emissions. If the
affected facility is located inside a building, determine an
observation location that is consistent with the requirements of the
applicable regulation (i.e., outside observation of emissions escaping
the building/structure or inside observation of emissions directly
emitted from the affected facility process unit). Then select a
position that enables a clear view of the potential emission point(s)
of the affected facility or of the building or structure housing the
affected facility, as appropriate for the applicable subpart. A
position at least 4.6 m (15 feet), but not more than 400 m (0.25
miles), from the emission source is recommended. For outdoor locations,
select a position where the sunlight is

[[Page 62038]]

not shining directly in the observer's eyes.
11.2 Field Records.
11.2.1 Outdoor Location. Record the following information on the
field data sheet (Figure 22-1): Company name, industry, process unit,
observer's name, observer's affiliation, and date. Record also the
estimated wind speed, wind direction, and sky condition. Sketch the
process unit being observed, and note the observer location relative to
the source and the sun. Indicate the potential and actual emission
points on the sketch.
11.2.2 Indoor Location. Record the following information on the
field data sheet (Figure 22-2): Company name, industry, process unit,
observer's name, observer's affiliation, and date. Record as
appropriate the type, location, and intensity of lighting on the data
sheet. Sketch the process unit being observed, and note the observer
location relative to the source. Indicate the potential and actual
fugitive emission points on the sketch.
11.3 Indoor Lighting Requirements. For indoor locations, use a
light meter to measure the level of illumination at a location as close
to the emission source(s) as is feasible. An illumination of greater
than 100 lux (10 foot candles) is considered necessary for proper
application of this method.
11.4 Observations.
11.4.1 Procedure. Record the clock time when observations begin.
Use one stopwatch to monitor the duration of the observation period.
Start this stopwatch when the observation period begins. If the
observation period is divided into two or more segments by process
shutdowns or observer rest breaks (see Section 11.4.3), stop the
stopwatch when a break begins and restart the stopwatch without
resetting it when the break ends. Stop the stopwatch at the end of the
observation period. The accumulated time indicated by this stopwatch is
the duration of observation period. When the observation period is
completed, record the clock time. During the observation period,
continuously watch the emission source. Upon observing an emission
(condensed water vapor is not considered an emission), start the second
accumulative stopwatch; stop the watch when the emission stops.
Continue this procedure for the entire observation period. The
accumulated elapsed time on this stopwatch is the total time emissions
were visible during the observation period (i.e., the emission time.)
11.4.2 Observation Period. Choose an observation period of
sufficient length to meet the requirements for determining compliance
with the emission standard in the applicable subpart of the
regulations. When the length of the observation period is specifically
stated in the applicable subpart, it may not be necessary to observe
the source for this entire period if the emission time required to
indicate noncompliance (based on the specified observation period) is
observed in a shorter time period. In other words, if the regulation
prohibits emissions for more than 6 minutes in any hour, then
observations may (optional) be stopped after an emission time of 6
minutes is exceeded. Similarly, when the regulation is expressed as an
emission frequency and the regulation prohibits emissions for greater
than 10 percent of the time in any hour, then observations may
(optional) be terminated after 6 minutes of emission are observed since
6 minutes is 10 percent of an hour. In any case, the observation period
shall not be less than 6 minutes in duration. In some cases, the
process operation may be intermittent or cyclic. In such cases, it may
be convenient for the observation period to coincide with the length of
the process cycle.
11.4.3 Observer Rest Breaks. Do not observe emissions continuously
for a period of more than 15 to 20 minutes without taking a rest break.
For sources requiring observation periods of greater than 20 minutes,
the observer shall take a break of not less than 5 minutes and not more
than 10 minutes after every 15 to 20 minutes of observation. If
continuous observations are desired for extended time periods, two
observers can alternate between making observations and taking breaks.
11.5 Recording Observations. Record the accumulated time of the
observation period on the data sheet as the observation period
duration. Record the accumulated time emissions were observed on the
data sheet as the emission time. Record the clock time the observation
period began and ended, as well as the clock time any observer breaks
began and ended.

12.0 Data Analysis and Calculations

If the applicable subpart requires that the emission rate be
expressed as an emission frequency (in percent), determine this value
as follows: Divide the accumulated emission time (in seconds) by the
duration of the observation period (in seconds) or by any minimum
observation period required in the applicable subpart, if the actual
observation period is less than the required period, and multiply this
quotient by 100.

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. Missan, R., and A. Stein. Guidelines for Evaluation of
Visible Emissions Certification, Field Procedures, Legal Aspects,
and Background Material. EPA Publication No. EPA-340/1-75-007. April
1975.
2. Wohlschlegel, P., and D.E. Wagoner. Guideline for Development
of a Quality Assurance Program: Volume IX-- Visual Determination of
Opacity Emissions from Stationary Sources. EPA Publication No. EPA-
650/4-74-005i. November 1975.
BILLING CODE 6560-50-P

[[Page 62039]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.354

[[Page 62040]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.355

BILLING CODE 6560-50-C

[[Page 62041]]

* * * * *

Method 24--Determination of Volatile Matter Content, Water Content,
Density, Volume Solids, and Weight Solids of Surface Coatings

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Volatile organic compounds Water.......... No CAS Number assigned 7732-
18-5
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of volatile matter content, water content, density, volume solids, and
weight solids of paint, varnish, lacquer, or other related surface
coatings.
1.3 Precision and Bias. Intra-and inter-laboratory analytical
precision statements are presented in Section 13.1. No bias has been
identified.

2.0 Summary of Method

2.1 Standard methods are used to determine the volatile matter
content, water content, density, volume solids, and weight solids of
paint, varnish, lacquer, or other related surface coatings.

3.0 Definitions

3.1 Waterborne coating means any coating which contains more than
5 percent water by weight in its volatile fraction.
3.2 Multicomponent coatings are coatings that are packaged in two
or more parts, which are combined before application. Upon combination
a coreactant from one part of the coating chemically reacts, at ambient
conditions, with a coreactant from another part of the coating.
3.3 Ultraviolet (UV) radiation-cured coatings are coatings which
contain unreacted monomers that are polymerized by exposure to
ultraviolet light.

4.0 Interferences. [Reserved]

5.0 Safety

5.1 Disclaimer. This method may involve hazardous materials,
operations, and equipment. This test method may not address all of the
safety problems associated with its use. It is the responsibility of
the user of this test method to establish appropriate safety and health
practices and to determine the applicability of regulatory limitations
prior to performing this test method.
5.2 Hazardous Components. Several of the compounds that may be
contained in the coatings analyzed by this method may be irritating or
corrosive to tissues (e.g., heptane) or may be toxic (e.g., benzene,
methyl alcohol). Nearly all are fire hazards. Appropriate precautions
can be found in reference documents, such as Reference 3 of Section
16.0.

6.0 Equipment and Supplies

The equipment and supplies specified in the ASTM methods listed in
Sections 6.1 through 6.6 (incorporated by reference--see Sec. 60.17 for
acceptable versions of the methods) are required:
6.1 ASTM D 1475-60, 80, or 90, Standard Test Method for Density of
Paint, Varnish, Lacquer, and Related Products.
6.2 ASTM D 2369-81, 87, 90, 92, 93, or 95, Standard Test Method
for Volatile Content of Coatings.
6.3 ASTM D 3792-79 or 91, Standard Test Method for Water Content
of Water Reducible Paints by Direct Injection into a Gas Chromatograph.
6.4 ASTM D 4017-81, 90, or 96a, Standard Test Method for Water in
Paints and Paint Materials by the Karl Fischer Titration Method.
6.5 ASTM 4457-85 91, Standard Test Method for Determination of
Dichloromethane and 1,1,1-Trichloroethane in Paints and Coatings by
Direct Injection into a Gas Chromatograph.
6.6 ASTM D 5403-93, Standard Test Methods for Volatile Content of
Radiation Curable Materials.

7.0 Reagents and Standards

7.1 The reagents and standards specified in the ASTM methods
listed in Sections 6.1 through 6.6 are required.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Follow the sample collection, preservation, storage, and
transport procedures described in Reference 1 of Section 16.0.

9.0 Quality Control

9.1 Reproducibility

Note:
Not applicable to UV radiation-cured coatings). The variety of
coatings that may be subject to analysis makes it necessary to
verify the ability of the analyst and the analytical procedures to
obtain reproducible results for the coatings tested. Verification is
accomplished by running duplicate analyses on each sample tested
(Sections 11.2 through 11.4) and comparing the results with the
intra-laboratory precision statements (Section 13.1) for each
parameter.

9.2 Confidence Limits for Waterborne Coatings. Because of the
inherent increased imprecision in the determination of the VOC content
of waterborne coatings as the weight percent of water increases,
measured parameters for waterborne coatings are replaced with
appropriate confidence limits (Section 12.6). These confidence limits
are based on measured parameters and inter-laboratory precision
statements.

10.0 Calibration and Standardization

10.1 Perform the calibration and standardization procedures
specified in the ASTM methods listed in Sections 6.1 through 6.6.

11.0 Analytical Procedure

Additional guidance can be found in Reference 2 of Section 16.0.
11.1 Non Thin-film Ultraviolet Radiation-cured (UV radiation-
cured) Coatings.
11.1.1 Volatile Content. Use the procedure in ASTM D 5403 to
determine the volatile matter content of the coating except the curing
test described in NOTE 2 of ASTM D 5403 is required.
11.1.2 Water Content. To determine water content, follow Section
11.3.2.
11.1.3 Coating Density. To determine coating density, follow
Section 11.3.3.
11.1.4 Solids Content. To determine solids content, follow Section
11.3.4.
11.1.5 To determine if a coating or ink can be classified as a
thin-film UV cured coating or ink, use the equation in Section 12.2. If
C is less than 0.2 g and A is greater than or equal to 225 cm\2\ (35
in\2\) then the coating or ink is considered a thin-film UV radiation-
cured coating and ASTM D 5403 is not applicable.

Note: As noted in Section 1.4 of ASTM D 5403, this method may
not be applicable to radiation curable materials wherein the
volatile material is water.

11.2 Multi-component Coatings.
11.2.1 Sample Preparation.
11.2.1.1 Prepare about 100 ml of sample by mixing the components
in a storage container, such as a glass jar with a screw top or a metal
can with a cap. The storage container should be just large enough to
hold the mixture. Combine the components (by weight or volume) in the
ratio recommended by the manufacturer. Tightly close the container
between additions and during mixing to prevent loss of volatile
materials. However, most manufacturers mixing instructions are by
volume. Because of possible error caused by expansion of the liquid
when measuring the volume, it is recommended that the components be
combined by weight. When weight is used to combine the components and
the manufacturer's recommended ratio is by volume, the density must be
determined by Section 11.3.3.

[[Page 62042]]

11.2.1.2 Immediately after mixing, take aliquots from this 100 ml
sample for determination of the total volatile content, water content,
and density.
11.2.2 Volatile Content. To determine total volatile content, use
the apparatus and reagents described in ASTM D2369 Sections 3 and 4
(incorporated by reference--see Sec. 60.17 for the approved versions of
the standard), respectively, and use the following procedures:
11.2.2.1 Weigh and record the weight of an aluminum foil weighing
dish. Add 3 1 ml of suitable solvent as specified in ASTM
D2369 to the weighing dish. Using a syringe as specified in ASTM D2369,
weigh to 1 mg, by difference, a sample of coating into the weighing
dish. For coatings believed to have a volatile content less than 40
weight percent, a suitable size is 0.3 + 0.10 g, but for coatings
believed to have a volatile content greater than 40 weight percent, a
suitable size is 0.5 0.1 g.

Note: If the volatile content determined pursuant to Section
12.4 is not in the range corresponding to the sample size chosen
repeat the test with the appropriate sample size. Add the specimen
dropwise, shaking (swirling) the dish to disperse the specimen
completely in the solvent. If the material forms a lump that cannot
be dispersed, discard the specimen and prepare a new one. Similarly,
prepare a duplicate. The sample shall stand for a minimum of 1 hour,
but no more than 24 hours prior to being oven cured at 110
5 deg.C (230 9 deg.F) for 1 hour.

11.2.2.2 Heat the aluminum foil dishes containing the dispersed
specimens in the forced draft oven for 60 min at 110
5 deg.C (230 9 deg.F). Caution--provide adequate
ventilation, consistent with accepted laboratory practice, to prevent
solvent vapors from accumulating to a dangerous level.
11.2.2.3 Remove the dishes from the oven, place immediately in a
desiccator, cool to ambient temperature, and weigh to within 1 mg.
11.2.2.4 Run analyses in pairs (duplicate sets) for each coating
mixture until the criterion in Section 11.4 is met. Calculate
WV following Equation 24-2 and record the arithmetic
average.
11.2.3 Water Content. To determine water content, follow Section
11.3.2.
11.2.4 Coating Density. To determine coating density, follow
Section 11.3.3.
11.2.5 Solids Content. To determine solids content, follow Section
11.3.4.
11.2.6 Exempt Solvent Content. To determine the exempt solvent
content, follow Section 11.3.5.

Note: For all other coatings (i.e., water-or solvent-borne
coatings) not covered by multicomponent or UV radiation-cured
coatings, analyze as shown below:

11.3 Water-or Solvent-borne coatings.
11.3.1 Volatile Content. Use the procedure in ASTM D 2369 to
determine the volatile matter content (may include water) of the
coating.
11.3.1.1 Record the following information:

W1 = weight of dish and sample before heating, g
W2 = weight of dish and sample after heating, g
W3 = sample weight, g.

11.3.1.2 Calculate the weight fraction of the volatile matter
(Wv) for each analysis as shown in Section 12.3.
11.3.1.3 Run duplicate analyses until the difference between the
two values in a set is less than or equal to the intra-laboratory
precision statement in Section 13.1.
11.3.1.4 Record the arithmetic average (Wv).
11.3.2 Water Content. For waterborne coatings only, determine the
weight fraction of water (Ww) using either ASTM D 3792 or
ASTM D 4017.
11.3.2.1 Run duplicate analyses until the difference between the
two values in a set is less than or equal to the intra-laboratory
precision statement in Section 13.1.
11.3.2.2 Record the arithmetic average (ww).
11.3.3 Coating Density. Determine the density (Dc, kg/l) of the
surface coating using the procedure in ASTM D 1475.
11.3.3.1 Run duplicate analyses until each value in a set deviates
from the mean of the set by no more than the intra-laboratory precision
statement in Section 13.1.
11.3.3.2 Record the arithmetic average (Dc).
11.3.4 Solids Content. Determine the volume fraction
(Vs) solids of the coating by calculation using the
manufacturer's formulation.
11.3.5 Exempt Solvent Content. Determine the weight fraction of
exempt solvents (WE) by using ASTM Method D4457. Run a
duplicate set of determinations and record the arithmetic average
(WE).
11.4 Sample Analysis Criteria. For Wv and
Ww, run duplicate analyses until the difference between the
two values in a set is less than or equal to the intra-laboratory
precision statement for that parameter. For Dc, run
duplicate analyses until each value in a set deviates from the mean of
the set by no more than the intra-laboratory precision statement. If,
after several attempts, it is concluded that the ASTM procedures cannot
be used for the specific coating with the established intra-laboratory
precision (excluding UV radiation-cured coatings), the U.S.
Environmental Protection Agency (EPA) will assume responsibility for
providing the necessary procedures for revising the method or precision
statements upon written request to: Director, Emissions, Monitoring,
and Analysis Division, MD-14, Office of Air Quality Planning and
Standards, U.S. Environmental Protection Agency, Research Triangle
Park, NC 27711.

12.0 Calculations and Data Analysis

12.1 Nomenclature.

A = Area of substrate, cm2, (in2).
C = Amount of coating or ink added to the substrate, g.
Dc = Density of coating or ink, g/cm\3\ (g/in\3\).
F = Manufacturer's recommended film thickness, cm (in).
Wo = Weight fraction of nonaqueous volatile matter, g/g.
Ws = Weight fraction of solids, g/g.
Wv = Weight fraction of the volatile matter, g/g.
Ww = Weight fraction of the water, g/g.
12.2 To determine if a coating or ink can be classified as a thin-
film UV cured coating or ink, use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.356

12.3 Calculate Wv for each analysis as shown below:
[GRAPHIC] [TIFF OMITTED] TR17OC00.357

12.4 Nonaqueous Volatile Matter.
12.4.1 Solvent-borne Coatings.
[GRAPHIC] [TIFF OMITTED] TR17OC00.358

12.4.2 Waterborne Coatings.
[GRAPHIC] [TIFF OMITTED] TR17OC00.359

12.4.3 Coatings Containing Exempt Solvents.
[GRAPHIC] [TIFF OMITTED] TR17OC00.360

12.5 Weight Fraction Solids.
[GRAPHIC] [TIFF OMITTED] TR17OC00.361

12.6 Confidence Limit Calculations for Waterborne Coatings. To
calculate the lower confidence limit, subtract the appropriate inter-
laboratory precision value from the measured mean value for that
parameter. To calculate the upper confidence limit, add the appropriate
inter-laboratory precision value to the measured mean value for that
parameter. For Wv and Dc, use the lower
confidence limits; for Ww, use the upper confidence limit.
Because Ws is calculated, there is no adjustment for this
parameter.

[[Continued on page 62043]]

Notices For
2009
2008
2007
2006
2005
2004
2003
2002
2001
2000
1999
1998
1997
1996
1995
1994

[[pp. 61993-62042]] Amendments for Testing and Monitoring Provisions

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