Section

[Code of Federal Regulations]
[Title 40, Volume 7]
[Revised as of July 1, 2005]
From the U.S. Government Printing Office via GPO Access
[CITE: 40CFR60.A6]

[Page 404]

Appendix A-6 to Part 60--Test Methods 16 through 18

Method 16--Semicontinuous determination of sulfur emissions from
stationary sources
Method 16A--Determination of total reduced sulfur emissions from
stationary sources (impinger technique)
Method 16B--Determination of total reduced sulfur emissions from
stationary sources

Method 17--Determination of particulate emissions from stationary
sources (in-stack filtration method)
Method 18--Measurement of gaseous organic compound emissions by gas
chromatography
The test methods in this appendix are referred to in Sec. 60.8
(Performance Tests) and Sec. 60.11 (Compliance With Standards and
Maintenance Requirements) of 40 CFR part 60, subpart A (General
Provisions). Specific uses of these test methods are described in the
standards of performance contained in the subparts, beginning with
Subpart D.
Within each standard of performance, a section title ``Test Methods
and Procedures'' is provided to: (1) Identify the test methods to be
used as reference methods to the facility subject to the respective
standard and (2) identify any special instructions or conditions to be
followed when applying a method to the respective facility. Such
instructions (for example, establish sampling rates, volumes, or
temperatures) are to be used either in addition to, or as a substitute
for procedures in a test method. Similarly, for sources subject to
emission monitoring requirements, specific instructions pertaining to
any use of a test method as a reference method are provided in the
subpart or in Appendix B.
Inclusion of methods in this appendix is not intended as an
endorsement or denial of their applicability to sources that are not
subject to standards of performance. The methods are potentially
applicable to other sources; however, applicability should be confirmed
by careful and appropriate evaluation of the conditions prevalent at
such sources.
The approach followed in the formulation of the test methods
involves specifications for equipment, procedures, and performance. In
concept, a performance specification approach would be preferable in all
methods because this allows the greatest flexibility to the user. In
practice, however, this approach is impractical in most cases because
performance specifications cannot be established. Most of the methods
described herein, therefore, involve specific equipment specifications
and procedures, and only a few methods in this appendix rely on
performance criteria.
Minor changes in the test methods should not necessarily affect the
validity of the results and it is recognized that alternative and
equivalent methods exist. Section 60.8 provides authority for the
Administrator to specify or approve (1) equivalent methods, (2)
alternative methods, and (3) minor changes in the methodology of the
test methods. It should be clearly understood that unless otherwise
identified all such methods and changes must have prior approval of the
Administrator. An owner employing such methods or deviations from the
test methods without obtaining prior approval does so at the risk of
subsequent disapproval and retesting with approved methods.
Within the test methods, certain specific equipment or procedures
are recognized as being acceptable or potentially acceptable and are
specifically identified in the methods. The items identified as
acceptable options may be used without approval but must be identified
in the test report. The potentially approvable options are cited as
``subject to the approval of the Administrator'' or as ``or
equivalent.'' Such potentially approvable techniques or alternatives may
be used at the discretion of the owner without prior approval. However,
detailed descriptions for applying these potentially approvable
techniques or alternatives are not provided in the test methods. Also,
the potentially approvable options are not necessarily acceptable in all
applications. Therefore, an owner electing to use such potentially
approvable techniques or alternatives is responsible for: (1) assuring
that the techniques or alternatives are in fact applicable and are
properly executed; (2) including a written description of the
alternative method in the test report (the written method must be clear
and must be capable of being performed without additional instruction,
and the degree of detail should be similar to the detail contained in
the test methods); and (3) providing any rationale or supporting data
necessary to show the validity of the alternative in the particular
application. Failure to meet these requirements can result in the
Administrator's disapproval of the alternative.

Method 16--Semicontinuous Determination of 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 thorough knowledge of at least
the following additional test methods: Method 1, Method 4, Method 15,
and Method 16A.

1.0 Scope and Application

1.1 Analytes.

[[Page 405]]

Hydrogen sulfide [H2S]......... 7783-06-4 50 ppb.
Methyl mercaptan [CH4S]........ 74-93-1 50 ppb.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of total reduced sulfur (TRS) compounds from recovery furnaces, lime
kilns, and smelt dissolving tanks at kraft pulp mills and fuel gas
combustion devices at petroleum refineries.

Note: The method described below uses the principle of gas
chromatographic (GC) separation and flame photometric detection (FPD).
Since there are many systems or sets of operating conditions that
represent useable methods of determining sulfur emissions, all systems
which employ this principle, but differ only in details of equipment and
operation, may be used as alternative methods, provided that the
calibration precision and sample line loss criteria are met.

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 gas sample is extracted from the emission source and an
aliquot is analyzed for hydrogen sulfide (H2S), methyl
mercaptan (MeSH), dimethyl sulfide (DMS), and dimethyl disulfide (DMDS)
by GC/FPD. These four compounds are known collectively as TRS.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Moisture. Moisture condensation in the sample delivery system,
the analytical column, or the FPD burner block can cause losses or
interferences. This is prevented by maintaining the probe, filter box,
and connections at a temperature of at least 120 [deg]C (248 [deg]F).
Moisture is removed in the SO2 scrubber and heating the
sample beyond this point is not necessary when the ambient temperature
is above 0 [deg]C (32 [deg]F). Alternatively, moisture may be eliminated
by heating the sample line, and by conditioning the sample with dry
dilution air to lower its dew point below the operating temperature of
the GC/FPD analytical system prior to analysis.
4.2 Carbon Monoxide (CO) and Carbon Dioxide (CO2). CO and
CO2 have a substantial desensitizing effect on the flame
photometric detector even after dilution. Acceptable systems must
demonstrate that they have eliminated this interference by some
procedure such as eluting these compounds before any of the compounds to
be measured. Compliance with this requirement can be demonstrated by
submitting chromatograms of calibration gases with and without
CO2 in the 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 10.2.
4.3 Particulate Matter. Particulate matter in gas samples can cause
interference by eventual clogging of the analytical system. This
interference is eliminated by using the Teflon filter after the probe.
4.4 Sulfur Dioxide (SO2). Sulfur dioxide is not a
specific interferant but may be present in such large amounts that it
cannot effectively be separated from the other compounds of interest.
The SO2 scrubber described in Section 6.1.3 will effectively
remove SO2 from the sample.

5.0 Safety

6.0 Equipment and Supplies

6.1. Sample Collection. The following items are needed for sample
collection.
6.1.1 Probe. Teflon or Teflon-lined stainless steel. The probe must
be heated to prevent moisture condensation. It must be designed to allow
calibration gas to enter the probe at or near the sample point entry.
Any portion of the probe that contacts the stack gas must be heated to
prevent moisture condensation. Figure 16-1 illustrates the probe used in
lime kilns and other sources where significant amounts of particulate
matter are present. The probe is designed with the deflector shield
placed between the sample and the gas inlet holes to reduce clogging of
the filter and possible adsorption of sample gas. As an alternative, the
probe described in Section 6.1.1 of Method 16A having a nozzle directed
away from the gas stream may be used at sources having significant
amounts of particulate matter.

[[Page 406]]

6.1.2 Particulate Filter. 50-mm Teflon filter holder and a 1- to 2-
micron porosity Teflon filter (available through Savillex Corporation,
5325 Highway 101, Minnetonka, Minnesota 55343). The filter holder must
be maintained in a hot box at a temperature of at least 120 [deg]C (248
[deg]F).
6.1.3 SO2 Scrubber. Three 300-ml Teflon segmented
impingers connected in series with flexible, thick-walled, Teflon
tubing. (Impinger parts and tubing available through Savillex.) The
first two impingers contain 100 ml of citrate buffer and the third
impinger is initially dry. The tip of the tube inserted into the
solution should be constricted to less than 3 mm (\1/8\ in.) ID and
should be immersed to a depth of at least 5 cm (2 in.). Immerse the
impingers in an ice water bath and maintain near 0 [deg]C (32 [deg]F).
The scrubber solution will normally last for a 3-hour run before needing
replacement. This will depend upon the effects of moisture and
particulate matter on the solution strength and pH. Connections between
the probe, particulate filter, and SO2 scrubber must be made
of Teflon and as short in length as possible. All portions of the probe,
particulate filter, and connections prior to the SO2 scrubber
(or alternative point of moisture removal) must be maintained at a
temperature of at least 120 [deg]C (248 [deg]F).
6.1.4 Sample Line. Teflon, no greater than 1.3 cm (\1/2\ in.) ID.
Alternative materials, such as virgin Nylon, may be used provided the
line loss test is acceptable.
6.1.5 Sample Pump. The sample pump must be a leakless Teflon-coated
diaphragm type or equivalent.
6.2 Analysis. The following items are needed for sample analysis:
6.2.1 Dilution System. Needed only for high sample concentrations.
The dilution system must be constructed such that all sample contacts
are made of Teflon, glass, or stainless steel.
6.2.2 Gas Chromatograph. The gas chromatograph must have at least
the following components:
6.2.2.1 Oven. Capable of maintaining the separation column at the
proper operating temperature 1 [deg]C (2 [deg]F).
6.2.2.2 Temperature Gauge. To monitor column oven, detector, and
exhaust temperature 1 [deg]C (2 [deg]F).
6.2.2.3 Flow System. Gas metering system to measure sample, fuel,
combustion gas, and carrier gas flows.
6.2.2.4 Flame Photometric Detector.
6.2.2.4.1 Electrometer. Capable of full scale amplification of
linear ranges of 10^-9 to 10^-4 amperes full scale.
6.2.2.4.2 Power Supply. Capable of delivering up to 750 volts.
6.2.2.4.3 Recorder. Compatible with the output voltage range of the
electrometer.
6.2.2.4.4 Rotary Gas Valves. Multiport Teflon-lined valves equipped
with sample loop. Sample loop volumes must be chosen to provide the
needed analytical range. Teflon tubing and fittings must be used
throughout to present an inert surface for sample gas. The gas
chromatograph must be calibrated with the sample loop used for sample
analysis.
6.2.3 Gas Chromatogram Columns. The column system must be
demonstrated to be capable of resolving the four major reduced sulfur
compounds: H2S, MeSH, DMS, and DMDS. It must also demonstrate
freedom from known interferences. To demonstrate that adequate
resolution has been achieved, submit a chromatogram of a calibration gas
containing all four of the TRS compounds in the concentration range of
the applicable standard. Adequate resolution will be defined as base
line separation of adjacent peaks when the amplifier attenuation is set
so that the smaller peak is at least 50 percent of full scale. Baseline
separation is defined as a return to zero 5
percent in the interval between peaks. Systems not meeting this criteria
may be considered alternate methods subject to the approval of the
Administrator.
6.3 Calibration. A calibration system, containing the following
components, is required (see Figure 16-2).
6.3.1 Tube Chamber. Chamber of glass or Teflon of sufficient
dimensions to house permeation tubes.
6.3.2 Flow System. To measure air flow over permeation tubes at
2 percent. Flow over the permeation device may
also be determined using a soap bubble flowmeter.
6.3.3 Constant Temperature Bath. Device capable of maintaining the
permeation tubes at the calibration temperature within 0.1 [deg]C (0.2
[deg]F).
6.3.4 Temperature Gauge. Thermometer or equivalent to monitor bath
temperature within 1 [deg]C (2 [deg]F).

7.0 Reagents and Standards

7.1 Fuel. Hydrogen (H2), prepurified grade or better.
7.2 Combustion Gas. Oxygen (O2) or air, research purity
or better.
7.3 Carrier Gas. Prepurified grade or better.
7.4 Diluent (if required). Air containing less than 50 ppb total
sulfur compounds and less than 10 ppmv each of moisture and total
hydrocarbons.
7.5 Calibration Gases
7.5.1 Permeation tubes, one each of H2S, MeSH, DMS, and
DMDS, gravimetrically calibrated and certified at some convenient
operating temperature. These tubes consist of hermetically sealed FEP
Teflon tubing in which a liquified gaseous substance is enclosed. The
enclosed gas permeates through the tubing wall at a constant rate. When
the temperature is constant, calibration gases

[[Page 407]]

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. These calibration gases are used to calibrate the GC/FPD
system and the dilution system.
7.5.2 Cylinder Gases. Cylinder gases may be used as alternatives to
permeation devices. The gases must be traceable to a primary standard
(such as permeation tubes) and not used beyond the certification
expiration date.
7.6 Citrate Buffer and Sample Line Loss Gas. Same as Method 15,
Sections 7.6 and 7.7.

8.0 Sample Collection, Preservation, Storage, and Transport

Same as Method 15, Section 8.0, except that the references to the
dilution system may not be applicable.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.0........................... Sample line loss Ensures that
check. uncorrected negative
bias introduced by
sample loss is no
greater than 20
percent, and
provides for
correction of bias
of 20 percent or
less.
8.0........................... Calibration drift Ensures that bias
test. introduced by drift
in the measurement
system output during
the run is no
greater than 5
percent.
10.0.......................... Analytical Ensures precision of
calibration. analytical results
within 5 percent.
------------------------------------------------------------------------

10.0 Calibration and Standardization

Same as Method 15, Section 10.0, with the following addition and
exceptions:
10.1 Use the four compounds that comprise TRS instead of the three
reduced sulfur compounds measured by Method 15.
10.2 Flow Meter. Calibration before each test run is recommended,
but not required; calibration following each test series is mandatory.
Calibrate each flow meter after each complete test series with a wet-
test meter. If the flow measuring device differs from the wet-test meter
by 5 percent or more, the completed test runs must be voided.
Alternatively, the flow data that yield the lower flow measurement may
be used. Flow over the permeation device may also be determined using a
soap bubble flowmeter.

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this method (see
Section 8.0).

12.0 Data Analysis and Calculations

12.1 Concentration of Reduced Sulfur Compounds. Calculate the
average concentration of each of the four analytes (i.e., DMDS, DMS,
H2S, and MeSH) over the sample run (specified in Section 8.2
of Method 15 as 16 injections).
[GRAPHIC] [TIFF OMITTED] TR17OC00.278

Where:

Si=Concentration of any reduced sulfur compound from the
i^th sample injection, ppm.
C=Average concentration of any one of the reduced sulfur compounds for
the entire run, ppm.
N=Number of injections in any run period.

12.2 TRS Concentration. Using Equation 16-2, calculate the TRS
concentration for each sample run.
[GRAPHIC] [TIFF OMITTED] TR17OC00.279

Where:

CTRS=TRS concentration, ppmv.
CH2S=Hydrogen sulfide concentration, ppmv.
CMeSH=Methyl mercaptan concentration, ppmv.
CDMS=Dimethyl sulfide concentration, ppmv.
CDMDS=Dimethyl disulfide concentration, ppmv.
d=Dilution factor, dimensionless.

12.3 Average TRS Concentration. Calculate the average TRS
concentration for all sample runs performed.
[GRAPHIC] [TIFF OMITTED] TR17OC00.280

Where:

[[Page 408]]

Average TRS=Average total reduced sulfur in ppm.
TRSi=Total reduced sulfur in ppm as determined by Equation
16-2.
N=Number of samples.
Bwo=Fraction of volume of water vapor in the gas stream as
determined by Method 4--Determination of Moisture in Stack Gases.

13.0 Method Performance

13.1 Analytical Range. The analytical range will vary with the
sample loop size. Typically, the analytical range may extend from 0.1 to
100 ppmv using 10- to 0.1-ml sample loop sizes. This eliminates the need
for sample dilution in most cases.
13.2 Sensitivity. Using the 10-ml sample size, the minimum
detectable concentration is approximately 50 ppb.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. O'Keeffe, A.E., and G.C. Ortman. ``Primary Standards for Trace
Gas Analysis.'' Analytical Chemical Journal, 38,76. 1966.
2. Stevens, R.K., A.E. O'Keeffe, and G.C. Ortman. ``Absolute
Calibration of a Flame Photometric Detector to Volatile Sulfur Compounds
at Sub-Part-Per-Million Levels.'' Environmental Science and Technology,
3:7. July 1969.
3. Mulik, J.D., R.K. Stevens, and R. Baumgardner. ``An Analytical
System Designed to Measure Multiple Malodorous Compounds Related to
Kraft Mill Activities.'' Presented at the 12th Conference on Methods in
Air Pollution and Industrial Hygiene Studies, University of Southern
California, Los Angeles, CA. April 6-8, 1971.
4. Devonald, R.H., R.S. Serenius, and A.D. McIntyre. ``Evaluation of
the Flame Photometric Detector for Analysis of Sulfur Compounds.'' Pulp
and Paper Magazine of Canada, 73,3. March 1972.
5. Grimley, K.W., W.S. Smith, and R.M. Martin. ``The Use of a
Dynamic Dilution System in the Conditioning of Stack Gases for Automated
Analysis by a Mobile Sampling Van.'' Presented at the 63rd Annual APCA
Meeting, St. Louis, MO. June 14-19, 1970.
6. General Reference. Standard Methods of Chemical Analysis, Volumes
III-A and III-B Instrumental Methods. Sixth Edition. Van Nostrand
Reinhold Co.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 409]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.281

[[Page 410]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.282

Method 16A--Determination of Total Reduced Sulfur Emissions From
Stationary Sources (Impinger Technique)

1.0 Scope and Application

1.1 Analytes.

[[Page 411]]

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Total reduced sulfur (TRS) N/A See Section 13.1.
including:
Dimethyl disulfide [(CH3)2S2]. 62-49-20
Dimethyl sulfide [(CH3)2S].... 75-18-3
Hydrogen sulfide [H2S]........ 7783-06-4
Methyl mercaptan [CH4S]....... 74-93-1
Reduced sulfur (RS) including: N/A
H2S........................... 7783-06-4
Carbonyl sulfide [COS]........ 463-58-1
Carbon disulfide [CS2]........ 75-15-0
Reported as: Sulfur dioxide (SO2). 7449-09-5
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of TRS emissions from recovery boilers, lime kilns, and smelt dissolving
tanks at kraft pulp mills, reduced sulfur compounds (H2S,
carbonyl sulfide, and carbon disulfide from sulfur recovery units at
onshore natural gas processing facilities, 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.
SO2 is removed selectively from the sample using a citrate
buffer solution. TRS compounds are then thermally oxidized to
SO2, collected in hydrogen peroxide as sulfate, and analyzed
by the Method 6 barium-thorin titration procedure.

3.0 Definitions [Reserved]

4.0 Interferences

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 Corrosive reagents. The following reagents are hazardous.
Personal protective equipment and safe procedures are useful in
preventing chemical splashes. If contact occurs, immediately flush with
copious amounts of water for at least 15 minutes. Remove clothing under
shower and decontaminate. Treat residual chemical burns as thermal
burns.
5.2.1 Hydrogen Peroxide (H2O2). Irritating to
eyes, skin, nose, and lungs.
5.2.2 Sodium Hydroxide (NaOH). Causes severe damage to eyes and
skin. Inhalation causes irritation to nose, throat, and lungs. Reacts
exothermically with limited amounts of water.
5.2.3 Sulfuric Acid (H2SO4). Rapidly
destructive to body tissue. Will cause third degree burns. Eye damage
may result in blindness. Inhalation may be fatal from spasm of the
larynx, usually within 30 minutes. May cause lung tissue damage with
edema. 3 mg/m\3\ will cause lung damage in uninitiated. 1 mg/m\3\ for 8
hours will cause lung damage or, in higher concentrations, death.
Provide ventilation to limit inhalation. Reacts violently with metals
and organics.
5.3 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 16A-1
and component parts are discussed below. Modifications to this sampling
train are acceptable provided the system performance check is met (see
Section 8.5).
6.1.1 Probe. Teflon tubing, 6.4-mm (\1/4\-in.) diameter,
sequentially wrapped with heat-resistant fiber strips, a rubberized heat
tape (plug at one end), and heat-resistant adhesive tape. A flexible
thermocouple or other suitable temperature measuring device

[[Page 412]]

should be placed between the Teflon tubing and the fiber strips so that
the temperature can be monitored to prevent softening of the probe. The
probe should be sheathed in stainless steel to provide in-stack
rigidity. A series of bored-out stainless steel fittings placed at the
front of the sheath will prevent moisture and particulate from entering
between the probe and sheath. A 6.4-mm (\1/4\-in.) Teflon elbow (bored
out) should be attached to the inlet of the probe, and a 2.54 cm (1 in.)
piece of Teflon tubing should be attached at the open end of the elbow
to permit the opening of the probe to be turned away from the
particulate stream; this will reduce the amount of particulate drawn
into the sampling train. The probe is depicted in Figure 16A-2.
6.1.2 Probe Brush. Nylon bristle brush with handle inserted into a
3.2-mm (\1/8\-in.) Teflon tubing. The Teflon tubing should be long
enough to pass the brush through the length of the probe.
6.1.3 Particulate Filter. 50-mm Teflon filter holder and a 1- to 2-
[micro]m porosity, Teflon filter (available through Savillex
Corporation, 5325 Highway 101, Minnetonka, Minnesota 55343). The filter
holder must be maintained in a hot box at a temperature sufficient to
prevent moisture condensation. A temperature of 121 [deg]C (250 [deg]F)
was found to be sufficient when testing a lime kiln under sub-freezing
ambient conditions.
6.1.4 SO2 Scrubber. Three 300-ml Teflon segmented
impingers connected in series with flexible, thick-walled, Teflon
tubing. (Impinger parts and tubing available through Savillex.) The
first two impingers contain 100 ml of citrate buffer and the third
impinger is initially dry. The tip of the tube inserted into the
solution should be constricted to less than 3 mm (\1/8\-in.) ID and
should be immersed to a depth of at least 5 cm (2 in.).
6.1.5 Combustion Tube. Quartz glass tubing with an expanded
combustion chamber 2.54 cm (1 in.) in diameter and at least 30.5 cm (12
in.) long. The tube ends should have an outside diameter of 0.6 cm (\1/
4\ in.) and be at least 15.3 cm (6 in.) long. This length is necessary
to maintain the quartz-glass connector near ambient temperature and
thereby avoid leaks. Alternatively, the outlet may be constructed with a
90-degree glass elbow and socket that would fit directly onto the inlet
of the first peroxide impinger.
6.1.6 Furnace. A furnace of sufficient size to enclose the
combustion chamber of the combustion tube with a temperature regulator
capable of maintaining the temperature at 800 100
[deg]C (1472 180 [deg]F). The furnace operating
temperature should be checked with a thermocouple to ensure accuracy.
6.1.7 Peroxide Impingers, Stopcock Grease, Temperature Sensor,
Drying Tube, Valve, Pump, and Barometer. Same as Method 6, Sections
6.1.1.2, 6.1.1.4, 6.1.1.5, 6.1.1.6, 6.1.1.7, 6.1.1.8, and 6.1.2,
respectively, except that the midget bubbler of Method 6, Section
6.1.1.2 is not required.
6.1.8 Vacuum Gauge. At least 760 mm Hg (30 in. Hg) gauge.
6.1.9 Rate Meter. Rotameter, or equivalent, accurate to within 5
percent at the selected flow rate of approximately 2 liters/min (4.2
ft\3\/hr).
6.1.10 Volume Meter. Dry gas meter capable of measuring the sample
volume under the sampling conditions of 2 liters/min (4.2 ft\3\/hr) with
an accuracy of 2 percent.
6.2 Sample Recovery. Polyethylene Bottles, 250-ml (one per sample).
6.3 Sample Preparation and Analysis. Same as Method 6, Section 6.3,
except a 10-ml buret with 0.05-ml graduations is required, and the
spectrophotometer is not needed.

7.0 Reagents and Standards

Note: Unless otherwise indicated, all reagents must conform to the
specifications established by the Committee on Analytical Reagents of
the American Chemical Society. When such specifications are not
available, the best available grade must be used.

7.1 Sample Collection. The following reagents are required for
sample analysis:
7.1.1 Water. Same as in Method 6, Section 7.1.1.
7.1.2 Citrate Buffer. Dissolve 300 g of potassium citrate (or 284 g
of sodium citrate) and 41 g of anhydrous citric acid in 1 liter of water
(200 ml is needed per test). Adjust the pH to between 5.4 and 5.6 with
potassium citrate or citric acid, as required.
7.1.3 Hydrogen Peroxide, 3 percent. Same as in Method 6, Section
7.1.3 (40 ml is needed per sample).
7.1.4 Recovery Check Gas. Hydrogen sulfide (100 ppmv or less) in
nitrogen, stored in aluminum cylinders. Verify the concentration by
Method 11 or by gas chromatography where the instrument is calibrated
with an H2S permeation tube as described below. For Method
11, the relative standard deviation should not exceed 5 percent on at
least three 20-minute runs.

Note: Alternatively, hydrogen sulfide recovery gas generated from a
permeation device gravimetrically calibrated and certified at some
convenient operating temperature may be used. The permeation rate of the
device must be such that at a dilution gas flow rate of 3 liters/min
(6.4 ft\3\/hr), an H2S concentration in the range of the
stack gas or within 20 percent of the standard can be generated.

7.1.5 Combustion Gas. Gas containing less than 50 ppb 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

[[Page 413]]

tube, and flow rate measuring device. Flow from a compressed air
cylinder is also acceptable.
7.2 Sample Recovery and Analysis. Same as Method 6, Sections 7.2.1
and 7.3, respectively.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Preparation of Sampling Train.
8.1.1 For the SO2 scrubber, measure 100 ml of citrate
buffer into the first and second impingers; leave the third impinger
empty. Immerse the impingers in an ice bath, and locate them as close as
possible to the filter heat box. The connecting tubing should be free of
loops. Maintain the probe and filter temperatures sufficiently high to
prevent moisture condensation, and monitor with a suitable temperature
sensor.
8.1.2 For the Method 6 part of the train, measure 20 ml of 3 percent
hydrogen peroxide into the first and second midget impingers. Leave the
third midget impinger empty, and place silica gel in the fourth midget
impinger. Alternatively, a silica gel drying tube may be used in place
of the fourth impinger. Maintain the oxidation furnace at 800 100 [deg]C (1472 180 [deg]F).
Place crushed ice and water around all impingers.
8.2 Citrate Scrubber Conditioning Procedure. Condition the citrate
buffer scrubbing solution by pulling stack gas through the Teflon
impingers and bypassing all other sampling train components. A purge
rate of 2 liters/min for 10 minutes has been found to be sufficient to
obtain equilibrium. After the citrate scrubber has been conditioned,
assemble the sampling train, and conduct (optional) a leak-check as
described in Method 6, Section 8.2.
8.3 Sample Collection. Same as in Method 6, Section 8.3, except the
sampling rate is 2 liters/min (10 percent) for 1
or 3 hours. After the sample is collected, remove the probe from the
stack, and conduct (mandatory) a post-test leak-check as described in
Method 6, Section 8.2. The 15-minute purge of the train following
collection should not be performed. After each 3-hour test run (or after
three 1-hour samples), conduct one system performance check (see Section
8.5) to determine the reduced sulfur recovery efficiency through the
sampling train. After this system performance check and before the next
test run, rinse and brush the probe with water, replace the filter, and
change the citrate scrubber (optional but recommended).

Note: In Method 16, a test run is composed of 16 individual analyses
(injects) performed over a period of not less than 3 hours or more than
6 hours. For Method 16A to be consistent with Method 16, the following
may be used to obtain a test run: (1) collect three 60-minute samples or
(2) collect one 3-hour sample. (Three test runs constitute a test.)

8.4 Sample Recovery. Disconnect the impingers. Quantitatively
transfer the contents of the midget impingers of the Method 6 part of
the train into a leak-free polyethylene bottle for shipment. Rinse the
three midget impingers and the connecting tubes with water and add the
washings to the same storage container. Mark the fluid level. Seal and
identify the sample container.
8.5 System Performance Check.
8.5.1 A system performance check is done (1) to validate the
sampling train components and procedure (prior to testing; optional) and
(2) to validate a test run (after a run). Perform a check in the field
prior to testing consisting of at least two samples (optional), and
perform an additional check after each 3 hour run or after three 1-hour
samples (mandatory).
8.5.2 The checks involve sampling a known concentration of
H2S and comparing the analyzed concentration with the known
concentration. Mix the H2S recovery check gas (Section 7.1.4)
and combustion gas in a dilution system such as that shown in Figure
16A-3. Adjust the flow rates to generate an H2S concentration
in the range of the stack gas or within 20 percent of the applicable
standard and an oxygen concentration greater than 1 percent at a total
flow rate of at least 2.5 liters/min (5.3 ft\3\/hr). Use Equation 16A-3
to calculate the concentration of recovery gas generated. Calibrate the
flow rate from both sources with a soap bubble flow meter so that the
diluted concentration of H2S can be accurately calculated.
8.5.3 Collect 30-minute samples, and analyze in the same manner as
the emission samples. Collect the sample through the probe of the
sampling train using a manifold or some other suitable device that will
ensure extraction of a representative sample.
8.5.4 The recovery check must be performed in the field prior to
replacing the SO2 scrubber and particulate filter and before
the probe is cleaned. Use Equation 16A-4 (see Section 12.5) to calculate
the recovery efficiency. Report the recovery efficiency with the
emission data; do not correct the emission data for the recovery
efficiency. A sample recovery of 100 20 percent
must be obtained for the emission data to be valid. However, if the
recovery efficiency is not in the 100 20 percent
range but the results do not affect the compliance or noncompliance
status of the affected facility, the Administrator may decide to accept
the results of the compliance test.

9.0 Quality Control

[[Page 414]]

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.5........................... System Ensure validity of
performance sampling train
check. components and
analytical
procedure.
8.2, 10.0..................... Sampling Ensure accurate
equipment leak- measurement of stack
check and gas flow rate,
calibration. sample volume.
10.0.......................... Barium standard Ensure precision of
solution normality
standardization. determination.
11.1.......................... Replicate Ensure precision of
titrations. titration
determinations.
11.2.......................... Audit sample Evaluate analyst's
analysis. technique and
standards
preparation.
------------------------------------------------------------------------

10.0 Calibration

Same as Method 6, Section 10.0.

11.0 Analytical Procedure

11.1 Sample Loss Check and Sample Analysis. Same as Method 6,
Sections 11.1 and 11.2, respectively, with the following exception: for
1-hour sampling, take a 40-ml aliquot, add 160 ml of 100 percent
isopropanol and four drops of thorin.
11.2 Audit Sample Analysis. Same as Method 6, Section 11.3.

12.0 Data Analysis and Calculations

In the calculations, at least one extra decimal figure should be
retained beyond that of the acquired data. Figures should be rounded off
after final calculations.
12.1 Nomenclature.

CTRS=Concentration of TRS as SO2, dry basis
corrected to standard conditions, ppmv.
CRG(act)=Actual concentration of recovery check gas (after
dilution), ppm.
CRG(m)=Measured concentration of recovery check gas
generated, ppm.
CH2S=Verified concentration of H2S recovery gas.
N=Normality of barium perchlorate titrant, milliequivalents/ml.
Pbar=Barometric pressure at exit orifice of the dry gas
meter, mm Hg (in. Hg).
Pstd=Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
QH2S=Calibrated flow rate of H2S recovery gas,
liters/min.
QCG=Calibrated flow rate of combustion gas, liters/min.
R=Recovery efficiency for the system performance check, percent.
Tm=Average dry gas meter absolute temperature, [deg]K
([deg]R).
Tstd=Standard absolute temperature, 293 [deg]K (528 [deg]R).
Va=Volume of sample aliquot titrated, ml.
Vm=Dry gas volume as measured by the dry gas meter, liters
(dcf).
Vm(std)=Dry gas volume measured by the dry gas meter,
corrected to standard conditions, liters (dscf).
Vsoln=Total volume of solution in which the sulfur dioxide
sample is contained, 100 ml.
Vt=Volume of barium perchlorate titrant used for the sample,
ml (average of replicate titrations).
Vtb=Volume of barium perchlorate titrant used for the blank,
ml.
Y=Dry gas meter calibration factor.
32.03=Equivalent weight of sulfur dioxide, mg/meq.

12.2 Dry Sample Gas Volume, Corrected to Standard Conditions.
[GRAPHIC] [TIFF OMITTED] TR17OC00.283

Where:

K1=0.3855 [deg]K/mm Hg for metric units,
=17.65 [deg]R/in. Hg for English units.

12.3 Concentration of TRS as ppm SO2.
[GRAPHIC] [TIFF OMITTED] TR17OC00.284

Where:

[[Page 415]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.285

12.4 Concentration of Recovery Gas Generated in the System
Performance Check.
[GRAPHIC] [TIFF OMITTED] TR17OC00.286

12.5 Recovery Efficiency for the System Performance Check.
[GRAPHIC] [TIFF OMITTED] TR17OC00.287

13.0 Method Performance

13.1 Analytical Range. The lower detectable limit is 0.1 ppmv
SO2 when sampling at 2 liters/min (4.2 ft\3\/hr) for 3 hours
or 0.3 ppmv when sampling at 2 liters/min (4.2 ft\3\/hr) for 1 hour. The
upper concentration limit of the method exceeds the TRS levels generally
encountered at kraft pulp mills.
13.2 Precision. Relative standard deviations of 2.0 and 2.6 percent
were obtained when sampling a recovery boiler for 1 and 3 hours,
respectively.
13.3 Bias.
13.3.1 No bias was found in Method 16A relative to Method 16 in a
separate study at a recovery boiler.
13.3.2 Comparison of Method 16A with Method 16 at a lime kiln
indicated that there was no bias in Method 16A. However, instability of
the source emissions adversely affected the comparison. The precision of
Method 16A at the lime kiln was similar to that obtained at the recovery
boiler (Section 13.2.1).
13.3.3 Relative standard deviations of 2.7 and 7.7 percent have been
obtained for system performance checks.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

As an alternative to the procedures specified in Section 7.1.4, the
following procedure may be used to verify the H2S
concentration of the recovery check gas.
16.1 Summary. The H2S is collected from the calibration
gas cylinder and is absorbed in zinc acetate solution to form zinc
sulfide. The latter compound is then measured iodometrically.
16.2 Range. The procedure has been examined in the range of 5 to
1500 ppmv.
16.3 Interferences. There are no known interferences to this
procedure when used to analyze cylinder gases containing H2S
in nitrogen.
16.4 Precision and Bias. Laboratory tests have shown a relative
standard deviation of less than 3 percent. The procedure showed no bias
when compared to a gas chromatographic method that used gravimetrically
certified permeation tubes for calibration.
16.5 Equipment and Supplies.
16.5.1 Sampling Apparatus. The sampling train is shown in Figure
16A-4. Its component parts are discussed in Sections 16.5.1.1 through
16.5.2.
16.5.1.1 Sampling Line. Teflon tubing (\1/4\-in.) to connect the
cylinder regulator to the sampling valve.
16.5.1.2 Needle Valve. Stainless steel or Teflon needle valve to
control the flow rate of gases to the impingers.
16.5.1.3 Impingers. Three impingers of approximately 100-ml
capacity, constructed to permit the addition of reagents through the gas
inlet stem. The impingers shall be connected in series with leak-free
glass or Teflon connectors. The impinger bottoms have a standard 24/25
ground-glass fitting. The stems are from standard 6.4-mm (\1/4\-in.)
ball joint midget impingers, custom lengthened by about 1 in. When
fitted together, the stem end should be approximately 1.27 cm (\1/2\
in.) from the bottom (Southern Scientific, Inc., Micanopy, Florida: Set
Number S6962-048). The third in-line impinger acts as a drop-out bottle.
16.5.1.4 Drying Tube, Rate Meter, and Barometer. Same as Method 11,
Sections 6.1.5, 6.1.8, and 6.1.10, respectively.
16.5.1.5 Cylinder Gas Regulator. Stainless steel, to reduce the
pressure of the gas stream entering the Teflon sampling line to a safe
level.
16.5.1.6 Soap Bubble Meter. Calibrated for 100 and 500 ml, or two
separate bubble meters.
16.5.1.7 Critical Orifice. For volume and rate measurements. The
critical orifice may be fabricated according to Section 16.7.3 and must
be calibrated as specified in Section 16.12.4.
16.5.1.8 Graduated Cylinder. 50-ml size.
16.5.1.9 Volumetric Flask. 1-liter size.
16.5.1.10 Volumetric Pipette. 15-ml size.

[[Page 416]]

16.5.1.11 Vacuum Gauge. Minimum 20 in. Hg capacity.
16.5.1.12 Stopwatch.
16.5.2 Sample Recovery and Analysis.
16.5.2.1 Erlenmeyer Flasks. 125- and 250-ml sizes.
16.5.2.2 Pipettes. 2-, 10-, 20-, and 100-ml volumetric.
16.5.2.3 Burette. 50-ml size.
16.5.2.4 Volumetric Flask. 1-liter size.
16.5.2.5 Graduated Cylinder. 50-ml size.
16.5.2.6 Wash Bottle.
16.5.2.7 Stirring Plate and Bars.
16.6 Reagents and Standards. Unless otherwise indicated, all
reagents must conform to the specifications established by the Committee
on Analytical Reagents of the American Chemical Society, where such
specifications are available. Otherwise, use the best available grade.
16.6.1 Water. Same as Method 11, Section 7.1.3.
16.6.2 Zinc Acetate Absorbing Solution. Dissolve 20 g zinc acetate
in water, and dilute to 1 liter.
16.6.3 Potassium Bi-iodate [KH(IO3)2]
Solution, Standard 0.100 N. Dissolve 3.249 g anhydrous
KH(IO3)2 in water, and dilute to 1 liter.
16.6.4 Sodium Thiosulfate (Na2S2O3)
Solution, Standard 0.1 N. Same as Method 11, Section 7.3.2. Standardize
according to Section 16.12.2.
16.6.5 Na2S2O3 Solution, Standard
0.01 N. Pipette 100.0 ml of 0.1 N
Na2S2O3 solution into a 1-liter
volumetric flask, and dilute to the mark with water.
16.6.6 Iodine Solution, 0.1 N. Same as Method 11, Section 7.2.3.
16.6.7 Standard Iodine Solution, 0.01 N. Same as in Method 11,
Section 7.2.4. Standardize according to Section 16.12.3.
16.6.8 Hydrochloric Acid (HCl) Solution, 10 Percent by Weight. Add
230 ml concentrated HCl (specific gravity 1.19) to 770 ml water.
16.6.9 Starch Indicator Solution. To 5 g starch (potato, arrowroot,
or soluble), add a little cold water, and grind in a mortar to a thin
paste. Pour into 1 liter of boiling water, stir, and let settle
overnight. Use the clear supernatant. Preserve with 1.25 g salicylic
acid, 4 g zinc chloride, or a combination of 4 g sodium propionate and 2
g sodium azide per liter of starch solution. Some commercial starch
substitutes are satisfactory.
16.7 Pre-test Procedures.
16.7.1 Selection of Gas Sample Volumes. This procedure has been
validated for estimating the volume of cylinder gas sample needed when
the H2S concentration is in the range of 5 to 1500 ppmv. The
sample volume ranges were selected in order to ensure a 35 to 60 percent
consumption of the 20 ml of 0.01 N iodine (thus ensuring a 0.01 N
Na2S2O3 titer of approximately 7 to 12
ml). The sample volumes for various H2S concentrations can be
estimated by dividing the approximate ppm-liters desired for a given
concentration range by the H2S concentration stated by the
manufacturer. For example, for analyzing a cylinder gas containing
approximately 10 ppmv H2S, the optimum sample volume is 65
liters (650 ppm-liters/10 ppmv). For analyzing a cylinder gas containing
approximately 1000 ppmv H2S, the optimum sample volume is 1
liter (1000 ppm-liters/1000 ppmv).

------------------------------------------------------------------------
Approximate
Approximate cylinder gas H2S concentration (ppmv) ppm-liters
desired
------------------------------------------------------------------------
5 to <30................................................ 650
30 to <500.............................................. 800
500 to <1500............................................ 1000
------------------------------------------------------------------------

16.7.2 Critical Orifice Flow Rate Selection. The following table
shows the ranges of sample flow rates that are desirable in order to
ensure capture of H2S in the impinger solution. Slight
deviations from these ranges will not have an impact on measured
concentrations.

------------------------------------------------------------------------
Critical orifice flow rate
Cylinder gas H2S concentration (ppmv) (ml/min)
------------------------------------------------------------------------
5 to 50 ppmv............................. 1500 500
50 to 250 ppmv........................... 500 250
250 to <1000 ppmv........................ 200 50
1000 ppmv..................... 75 25
------------------------------------------------------------------------

16.7.3 Critical Orifice Fabrication. Critical orifice of desired
flow rates may be fabricated by selecting an orifice tube of desired
length and connecting \1/16\-in.x\1/4\-in. (0.16 cmx0.64 cm) reducing
fittings to both ends. The inside diameters and lengths of orifice tubes
needed to obtain specific flow rates are shown below.

----------------------------------------------------------------------------------------------------------------
Flowrate (ml/ Altech
Tube (in. OD) Tube (in. ID) Length (in.) min) Catalog No.
----------------------------------------------------------------------------------------------------------------
\1/16\.......................................... 0.007 1.2 85 301430
\1/16\.......................................... 0.01 3.2 215 300530
\1/16\.......................................... 0.01 1.2 350 300530
\1/16\.......................................... 0.02 1.2 1400 300230
----------------------------------------------------------------------------------------------------------------

16.7.4 Determination of Critical Orifice Approximate Flow Rate.
Connect the critical orifice to the sampling system as shown in Figure
16A-4 but without the H2S cylinder.

[[Page 417]]

Connect a rotameter in the line to the first impinger. Turn on the pump,
and adjust the valve to give a reading of about half atmospheric
pressure. Observe the rotameter reading. Slowly increase the vacuum
until a stable flow rate is reached, and record this as the critical
vacuum. The measured flow rate indicates the expected critical flow rate
of the orifice. If this flow rate is in the range shown in Section
16.7.2, proceed with the critical orifice calibration according to
Section 16.12.4.
16.7.5 Determination of Approximate Sampling Time. Determine the
approximate sampling time for a cylinder of known concentration. Use the
optimum sample volume obtained in Section 16.7.1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.288

16.8 Sample Collection.
16.8.1 Connect the Teflon tubing, Teflon tee, and rotameter to the
flow control needle valve as shown in Figure 16A-4. Vent the rotameter
to an exhaust hood. Plug the open end of the tee. Five to 10 minutes
prior to sampling, open the cylinder valve while keeping the flow
control needle valve closed. Adjust the delivery pressure to 20 psi.
Open the needle valve slowly until the rotameter shows a flow rate
approximately 50 to 100 ml above the flow rate of the critical orifice
being used in the system.
16.8.2 Place 50 ml of zinc acetate solution in two of the impingers,
connect them and the empty third impinger (dropout bottle) and the rest
of the equipment as shown in Figure 16A-4. Make sure the ground-glass
fittings are tight. The impingers can be easily stabilized by using a
small cardboard box in which three holes have been cut, to act as a
holder. Connect the Teflon sample line to the first impinger. Cover the
impingers with a dark cloth or piece of plastic to protect the absorbing
solution from light during sampling.
16.8.3 Record the temperature and barometric pressure. Note the gas
flow rate through the rotameter. Open the closed end of the tee. Connect
the sampling tube to the tee, ensuring a tight connection. Start the
sampling pump and stopwatch simultaneously. Note the decrease in flow
rate through the excess flow rotameter. This decrease should equal the
known flow rate of the critical orifice being used. Continue sampling
for the period determined in Section 16.7.5.
16.8.4 When sampling is complete, turn off the pump and stopwatch.
Disconnect the sampling line from the tee and plug it. Close the needle
valve followed by the cylinder valve. Record the sampling time.
16.9 Blank Analysis. While the sample is being collected, run a
blank as follows: To a 250-ml Erlenmeyer flask, add 100 ml of zinc
acetate solution, 20.0 ml of 0.01 N iodine solution, and 2 ml HCl
solution. Titrate, while stirring, with 0.01 N
Na2S2O3 until the solution is light
yellow. Add starch, and continue titrating until the blue color
disappears. Analyze a blank with each sample, as the blank titer has
been observed to change over the course of a day.

Note: Iodine titration of zinc acetate solutions is difficult to
perform because the solution turns slightly white in color near the end
point, and the disappearance of the blue color is hard to recognize. In
addition, a blue color may reappear in the solution about 30 to 45
seconds after the titration endpoint is reached. This should not be
taken to mean 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:

[[Page 418]]

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.
[GRAPHIC] [TIFF OMITTED] TR17OC00.289

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.
[thetas]s=Sampling time, min.
[thetas]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).
[GRAPHIC] [TIFF OMITTED] TR17OC00.290

16.13.3 Normality of Standard Iodine Solution (0.01 N).

[[Page 419]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.291

16.13.4 Sample Gas Volume.
[GRAPHIC] [TIFF OMITTED] TR17OC00.292

16.13.5 Concentration of H2S in the Gas Cylinder.

17.0 References
[GRAPHIC] [TIFF OMITTED] TR17OC00.293

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.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 420]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.294

[[Page 421]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.295

[[Page 422]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.296

[[Page 423]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.297

Date____________________________________________________________________
Critical orifice ID_____________________________________________________
Soap bubble meter volume, Vsb---- liters
Time, [thetas]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,

[[Page 424]]

[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

[[Page 425]]

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

[[Page 426]]

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.
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.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 427]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.301

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

1.0 Scope and Application

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

[[Page 428]]

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.

[[Page 429]]

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 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

[[Page 430]]

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.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 431]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.302

[[Page 432]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.303

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

[[Page 433]]

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.

[[Page 434]]

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 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

[[Page 435]]

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 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

[[Page 436]]

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

[[Page 437]]

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 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

[[Page 438]]

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 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

[[Page 439]]

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, 0.70<=R<=1.30 (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 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

[[Page 440]]

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, [micro]l.
M=Molecular weight of organic, g/g-mole.
ms=Total mass of compound measured on adsorbent with spiked
train ([micro]g).
mu=Total mass of compound measured on adsorbent with unspiked
train ([micro]g).
mv=Mass per volume of spiked compound measured ([micro]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
([micro]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.
[micro]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.

[[Page 441]]

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

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:

[[Page 442]]

[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.

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.

[[Page 443]]

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

[[Page 444]]

analyzing the gas by GC at high sensitivity. Experience indicates that
it is desirable to allow the inert gas to remain in the bag about 24
hours or longer to check for desorption of organics from the bag. Follow
the leak-check and sample collection procedures given in Section 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.

[[Page 445]]

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________________________________________________
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
Compound data:
Compound and Retention time and Attenuation
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________

Figure 18-2. Chromatographic Conditions Data Sheet

[[Page 446]]

Figure 18-3. Preparation of Standards in Tedlar Bags and Calibration Curve
----------------------------------------------------------------------------------------------------------------
Standards
-----------------------------------------------------
Mixture 1 i>2 i>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)
----------------------------------------------------------------------------------------------------------------

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

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

Calibration Device
----------------------------------------------------------------------------------------------------------------
Time (min) Gas volume a Flow rate b
----------------------------------------------------------------------------------------------------------------

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

[[Page 447]]

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

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

[[Page 448]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.314

[[Page 449]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.315

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
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)

[[Page 450]]

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
[GRAPHIC] [TIFF OMITTED] TR17OC00.316

[[Page 451]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.317

[[Page 452]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.318

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

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

[[Page 453]]

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

[[Page 454]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.319

[[Page 455]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.320

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

Date

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

[[Page 456]]

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

[36 FR 24877, Dec. 23, 1971]

Editorial Note: For Federal Register citations affecting part 60,
appendix A-6, see the List of CFR Sections Affected, which appears in
the Finding Aids section of the printed volume and on GPO Access.