[[pp. 62043-62092]] Amendments for Testing and Monitoring Provisions

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

[Federal Register: October 17, 2000 (Volume 65, Number 201)]
[Rules and Regulations]
[Page 62043-62092]
From the Federal Register Online via GPO Access [wais.access.gpo.gov]
[DOCID:fr17oc00-16]

[[Continued from page 62042]]

[[Page 62043]]

13.0 Method Performance

13.1 Analytical Precision Statements. The intra-and inter-
laboratory precision statements are given in Table 24-1 in Section
17.0.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

Same as specified in Section 6.0, with the addition of the
following:
1. Standard Procedure for Collection of Coating and Ink Samples for
Analysis by Reference Methods 24 and 24A. EPA-340/1-91-010. U.S.
Environmental Protection Agency, Stationary Source Compliance Division,
Washington, D.C. September 1991.
2. Standard Operating Procedure for Analysis of Coating and Ink
Samples by Reference Methods 24 and 24A.
EPA-340/1-91-011. U.S. Environmental Protection Agency, Stationary
Source Compliance Division, Washington, D.C. September 1991.
3. Handbook of Hazardous Materials: Fire, Safety, Health. Alliance
of American Insurers. Schaumberg, IL. 1983.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

Table 24-1.--Analytical Precision Statements
----------------------------------------------------------------------------------------------------------------
Intra-laboratory Inter-laboratory
----------------------------------------------------------------------------------------------------------------
Volatile matter content, Wv............ 0.015 Wv.............. 0.047 W8v
Water content, Ww...................... 0.029 W8w............. 0.075 Ww
Density, Dc............................ 0.001 kg/l............ 0.002 kg/l
----------------------------------------------------------------------------------------------------------------

Method 24A--Determination of Volatile Matter Content and Density of
Publication Rotogravure Inks and Related Publication Rotogravure
Coatings

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Volatile organic compounds (VOC).......... No CAS number assigned.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of the VOC content and density of solvent-borne (solvent-reducible)
publication rotogravure inks and related publication rotogravure
coatings.

2.0 Summary of Method

2.1 Separate procedures are used to determine the VOC weight
fraction and density of the ink or related coating and the density of
the solvent in the ink or related coating. The VOC weight fraction is
determined by measuring the weight loss of a known sample quantity
which has been heated for a specified length of time at a specified
temperature. The density of both the ink or related coating and solvent
are measured by a standard procedure. From this information, the VOC
volume fraction is calculated.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

5.1 Disclaimer. This method may involve hazardous materials,
operations, and equipment. This test method does not purport to address
all of the safety problems associated with its use. It is the
responsibility of the user of this test method to establish appropriate
safety and health practices and to determine the applicability of
regulatory limitations prior to performing this test method.
5.2 Hazardous Components. Some of the compounds that may be
contained in the inks or related coatings analyzed by this method may
be irritating or corrosive to tissues or may be toxic. Nearly all are
fire hazards. Appropriate precautions can be found in reference
documents, such as Reference 6 of Section 16.0.

6.0 Equipment and Supplies

The following equipment and supplies are required for sample
analysis:
6.1 Weighing Dishes. Aluminum foil, 58 mm (2.3 in.) in diameter by
18 mm (0.7 in.) high, with a flat bottom. There must be at least three
weighing dishes per sample.
6.2 Disposable Syringe. 5 ml.
6.3 Analytical Balance. To measure to within 0.1 mg.
6.4 Oven. Vacuum oven capable of maintaining a temperature of 120
2 deg.C (248 4 deg.F) and an absolute
pressure of 510 51 mm Hg (20 2 in. Hg) for 4
hours. Alternatively, a forced draft oven capable of maintaining a
temperature of 120 2 deg.C (248 4 deg.F)
for 24 hours.
6.5 The equipment and supplies specified in ASTM D 1475-60, 80, or
90 (incorporated by reference--see Sec. 60.17).

7.0 Reagents and Standards

7.1 The reagents and standards specified in ASTM D 1475-60, 80, or
90 are required.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Follow the sample collection, preservation, storage, and
transport procedures described in Reference 4 of Section 16.0.

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedure

Additional guidance can be found in Reference 5 of Section 16.0.
11.1 VOC Weight Fraction. Shake or mix the ink or related coating
sample thoroughly to assure that all the solids are completely
suspended. Label and weigh to the nearest 0.1 mg a weighing dish and
record this weight (Mx1). Using a 5 ml syringe, without a
needle, extract an aliquot from the ink or related coating sample.
Weigh the syringe and aliquot to the nearest 0.1 mg and record this
weight (Mcy1). Transfer 1 to 3 g of the aliquot to the tared
weighing dish. Reweigh the syringe and remaining aliquot to the nearest
0.1 mg and record this weight (Mcy2). Heat the weighing dish
with the transferred aliquot in a vacuum oven at an absolute pressure
of 510 51 mm Hg (20 2 in. Hg) and a
temperature of 120 2 deg.C (248 4 deg.F)
for 4 hours. Alternatively, heat the weighing dish with the transferred
aliquot in a forced draft oven at a temperature of 120 2
deg.C for 24 hours. After the weighing dish has cooled, reweigh it to
the nearest 0.1 mg and record the weight (Mx2). Repeat this
procedure two times for each ink or related coating sample, for a total
of three samples.
11.2 Ink or Related Coating Density. Determine the density of the
ink or related coating (Dc) according to the procedure
outlined in ASTM D 1475. Make a total of three determinations for each
ink or related coating sample. Report the ink or related coating
density as the arithmetic average (Dc) of the three
determinations.
11.3 Solvent Density. Determine the density of the solvent
(Do) according to

[[Page 62044]]

the procedure outlined in ASTM D 1475. Make a total of three
determinations for each ink or related coating sample. Report the
solvent density as the arithmetic average (Do) of the three
determinations.

12.0 Calculations and Data Analysis

12.1 VOC Weight Fraction. For each determination, calculate the
volatile organic content weight fraction (Wo) using the
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.362

Make a total of three determinations. Report the VOC weight fraction as
the arithmetic average (Wo) of the three determinations.
12.2 VOC Volume Fraction. Calculate the volume fraction volatile
organic content (Vo) using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.363

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Standard Test Method for Density of Paint, Varnish, Lacquer,
and Related Products. ASTM Designation D 1475.
2. Teleconversation. Wright, Chuck, Inmont Corporation with
Reich, R., A., Radian Corporation. September 25, 1979, Gravure Ink
Analysis.
3. Teleconversation. Oppenheimer, Robert, Gravure Research
Institute with Burt, Rick, Radian Corporation, November 5, 1979,
Gravure Ink Analysis.
4. Standard Procedure for Collection of Coating and Ink Samples
for Analysis by Reference Methods 24 and 24A. EPA-340/1-91-010. U.S.
Environmental Protection Agency, Stationary Source Compliance
Division, Washington, D.C. September 1991.
5. Standard Operating Procedure for Analysis of Coating and Ink
Samples by Reference Methods 24 and 24A. EPA-340/1-91-011. U.S.
Environmental Protection Agency, Stationary Source Compliance
Division, Washington, D.C. September 1991.
6. Handbook of Hazardous Materials: Fire, Safety, Health.
Alliance of American Insurers. Schaumberg, IL. 1983.

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

Method 25--Determination of Total Gaseous Nonmethane Organic
Emissions as Carbon

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Total gaseous nonmethane organic N/A Dependent upon
compounds (TGNMO). analytical
equipment.
------------------------------------------------------------------------

1.2 Applicability.
1.2.1 This method is applicable for the determination of volatile
organic compounds (VOC) (measured as total gaseous nonmethane organics
(TGNMO) and reported as carbon) in stationary source emissions. This
method is not applicable for the determination of organic particulate
matter.
1.2.2 This method is not the only method that applies to the
measurement of VOC. Costs, logistics, and other practicalities of
source testing may make other test methods more desirable for measuring
VOC contents of certain effluent streams. Proper judgment is required
in determining the most applicable VOC test method. For example,
depending upon the molecular composition of the organics in the
effluent stream, a totally automated semicontinuous nonmethane organics
(NMO) analyzer interfaced directly to the source may yield accurate
results. This approach has the advantage of providing emission data
semicontinuously over an extended time period.
1.2.3 Direct measurement of an effluent with a flame ionization
detector (FID) analyzer may be appropriate with prior characterization
of the gas stream and knowledge that the detector responds predictably
to the organic compounds in the stream. If present, methane
(CH4) will, of course, also be measured. The FID can be used
under any of the following limited conditions: (1) Where only one
compound is known to exist; (2) when the organic compounds consist of
only hydrogen and carbon; (3) where the relative percentages of the
compounds are known or can be determined, and the FID responses to the
compounds are known; (4) where a consistent mixture of the compounds
exists before and after emission control and only the relative
concentrations are to be assessed; or (5) where the FID can be
calibrated against mass standards of the compounds emitted (solvent
emissions, for example).
1.2.4 Another example of the use of a direct FID is as a screening
method. If there is enough information available to provide a rough
estimate of the analyzer accuracy, the FID analyzer can be used to
determine the VOC content of an uncharacterized gas stream. With a
sufficient buffer to account for possible inaccuracies, the direct FID
can be a useful tool to obtain the desired results without costly exact
determination.
1.2.5 In situations where a qualitative/quantitative analysis of
an

[[Page 62045]]

effluent stream is desired or required, a gas chromatographic FID
system may apply. However, for sources emitting numerous organics, the
time and expense of this approach will be formidable.

2.0 Summary of Method

2.1 An emission sample is withdrawn from the stack at a constant
rate through a heated filter and a chilled condensate trap by means of
an evacuated sample tank. After sampling is completed, the TGNMO are
determined by independently analyzing the condensate trap and sample
tank fractions and combining the analytical results. The organic
content of the condensate trap fraction is determined by oxidizing the
NMO to carbon dioxide (CO2) and quantitatively collecting in
the effluent in an evacuated vessel; then a portion of the
CO2 is reduced to CH4 and measured by an FID. The
organic content of the sample tank fraction is measured by injecting a
portion of the sample into a gas chromatographic column to separate the
NMO from carbon monoxide (CO), CO2, and CH4; the
NMO are oxidized to CO2, reduced to CH4, and
measured by an FID. In this manner, the variable response of the FID
associated with different types of organics is eliminated.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Carbon Dioxide and Water Vapor. When carbon dioxide
(CO2) and water vapor are present together in the stack,
they can produce a positive bias in the sample. The magnitude of the
bias depends on the concentrations of CO2 and water vapor.
As a guideline, multiply the CO2 concentration, expressed as
volume percent, times the water vapor concentration. If this product
does not exceed 100, the bias can be considered insignificant. For
example, the bias is not significant for a source having 10 percent
CO2 and 10 percent water vapor, but it might be significant
for a source having 10 percent CO2 and 20 percent water
vapor.
4.2. Particulate Matter. Collection of organic particulate matter
in the condensate trap would produce a positive bias. A filter is
included in the sampling equipment to minimize this bias.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. The sampling system consists of a heated
probe, heated filter, condensate trap, flow control system, and sample
tank (see Figure 25-1). The TGNMO sampling equipment can be constructed
from commercially available components and components fabricated in a
machine shop. The following equipment is required:
6.1.1 Heated Probe. 6.4-mm (\1/4\-in.) OD stainless steel tubing
with a heating system capable of maintaining a gas temperature at the
exit end of at least 129 deg.C (265 deg.F). The probe shall be
equipped with a temperature sensor at the exit end to monitor the gas
temperature. A suitable probe is shown in Figure 25-1. The nozzle is an
elbow fitting attached to the front end of the probe while the
temperature sensor is inserted in the side arm of a tee fitting
attached to the rear of the probe. The probe is wrapped with a suitable
length of high temperature heating tape, and then covered with two
layers of glass cloth insulation and one layer of aluminum foil or an
equivalent wrapping.

Note: If it is not possible to use a heating system for safety
reasons, an unheated system with an in-stack filter is a suitable
alternative.

6.1.2 Filter Holder. 25-mm (\15/16\-in.) ID Gelman filter holder
with 303 stainless steel body and 316 stainless steel support screen
with the Viton O-ring replaced by a Teflon O-ring.
6.1.3 Filter Heating System.
6.1.3.1 A metal box consisting of an inner and an outer shell
separated by insulating material with a heating element in the inner
shell capable of maintaining a gas temperature at the filter of 121
3 deg.C (250 5 deg.F). The heating box
shall include temperature sensors to monitor the gas temperature
immediately upstream and immediately downstream of the filter.
6.1.3.2 A suitable heating box is shown in Figure 25-2. The outer
shell is a metal box that measures 102 mm x 280 mm x 292 mm (4 in. x 11
in. x 11\1/2\ in.), while the inner shell is a metal box measuring 76
mm x 229 mm x 241 mm (3 in. x 9 in. x 9\1/2\ in.). The inner box is
supported by 13-mm (\1/2\-in.) phenolic rods. The void space between
the boxes is filled with ceramic fiber insulation which is sealed in
place by means of a silicon rubber bead around the upper sides of the
box. A removable lid made in a similar manner, with a 25-mm (1-in.) gap
between the parts is used to cover the heating chamber. The inner box
is heated with a 250-watt cartridge heater, shielded by a stainless
steel shroud. The heater is regulated by a thermostatic temperature
controller which is set to maintain a gas temperature of 121 deg.C
(250 deg.F) as measured by the temperature sensor upstream of the
filter.

Note: If it is not possible to use a heating system for safety
reasons, an unheated system with an in-stack filter is a suitable
alternative.

6.1.4 Condensate Trap. 9.5-mm (\3/8\-in.) OD 316 stainless steel
tubing bent into a U-shape. Exact dimensions are shown in Figure 25-3.
The tubing shall be packed with coarse quartz wool, to a density of
approximately 0.11 g/cm\3\ before bending. While the condensate trap is
packed with dry ice in the Dewar, an ice bridge may form between the
arms of the condensate trap making it difficult to remove the
condensate trap. This problem can be prevented by attaching a steel
plate between the arms of the condensate trap in the same plane as the
arms to completely fill the intervening space.
6.1.5 Valve. Stainless steel control valve for starting and
stopping sample flow.
6.1.6 Metering Valve. Stainless steel valve for regulating the
sample flow rate through the sample train.
6.1.7 Rate Meter. Rotameter, or equivalent, capable of measuring
sample flow in the range of 60 to 100 cm\3\/min (0.13 to 0.21 ft\3\/
hr).
6.1.8 Sample Tank. Stainless steel or aluminum tank with a minimum
volume of 4 liters (0.14 ft\3\).

Note: Sample volumes greater than 4 liters may be required for
sources with low organic concentrations.

6.1.9 Mercury Manometer. U-tube manometer or absolute pressure
gauge capable of measuring pressure to within 1 mm Hg in the range of 0
to 900 mm.
6.1.10 Vacuum Pump. Capable of evacuating to an absolute pressure
of 10 mm Hg.
6.2 Condensate Recovery. The system for the recovery of the
organics captured in the condensate trap consists of a heat source, an
oxidation catalyst, a nondispersive infrared (NDIR) analyzer, and an
intermediate collection vessel (ICV). Figure 25-4 is a schematic of a
typical system. The system shall be capable of proper oxidation and
recovery, as specified in Section 10.1.1. The following major
components are required:
6.2.1 Heat Source. Sufficient to heat the condensate trap
(including probe) to a temperature of 200 deg.C (390 deg.F). A system
using both a heat gun and an electric tube furnace is recommended.

[[Page 62046]]

6.2.2 Heat Tape. Sufficient to heat the connecting tubing between
the water trap and the oxidation catalyst to 100 deg.C (212 deg.F).
6.2.3 Oxidation Catalyst. A suitable length of 9.5 mm (\3/8\-in.)
OD Inconel 600 tubing packed with 15 cm (6 in.) of 3.2 mm (\3/8\-in.)
diameter 19 percent chromia on alumina pellets. The catalyst material
is packed in the center of the catalyst tube with quartz wool packed on
either end to hold it in place.
6.2.4 Water Trap. Leak-proof, capable of removing moisture from
the gas stream.
6.2.5 Syringe Port. A 6.4-mm (\1/4\-in.) OD stainless steel tee
fitting with a rubber septum placed in the side arm.
6.2.6 NDIR Detector. Capable of indicating CO2
concentration in the range of zero to 5 percent, to monitor the
progress of combustion of the organic compounds from the condensate
trap.
6.2.7 Flow-Control Valve. Stainless steel, to maintain the trap
conditioning system near atmospheric pressure.
6.2.8 Intermediate Collection Vessel. Stainless steel or aluminum,
equipped with a female quick connect. Tanks with nominal volumes of at
least 6 liters (0.2 ft\3\) are recommended.
6.2.9 Mercury Manometer. Same as described in Section 6.1.9.
6.2.10 Syringe. 10-ml gas-tight glass syringe equipped with an
appropriate needle.
6.2.11 Syringes. 10-l and 50-l liquid injection
syringes.
6.2.12 Liquid Sample Injection Unit. 316 Stainless steel U-tube
fitted with an injection septum (see Figure 25-7).
6.3 Analysis.
6.3.1 NMO Analyzer. The NMO analyzer is a gas chromatograph (GC)
with backflush capability for NMO analysis and is equipped with an
oxidation catalyst, reduction catalyst, and FID. Figures 25-5 and 25-6
are schematics of a typical NMO analyzer. This semicontinuous GC/FID
analyzer shall be capable of: (1) Separating CO, CO2, and
CH4 from NMO, (2) reducing the CO2 to
CH4 and quantifying as CH4, and (3) oxidizing the
NMO to CO2, reducing the CO2 to CH4
and quantifying as CH4, according to Section 10.1.2. The
analyzer consists of the following major components:
6.3.1.1 Oxidation Catalyst. A suitable length of 9.5-mm (\3/8\-
in.) OD Inconel 600 tubing packed with 5.1 cm (2 in.) of 19 percent
chromia on 3.2-mm (\1/8\-in.) alumina pellets. The catalyst material is
packed in the center of the tube supported on either side by quartz
wool. The catalyst tube must be mounted vertically in a 650 deg.C
(1200 deg.F) furnace. Longer catalysts mounted horizontally may be
used, provided they can meet the specifications of Section 10.1.2.1.
6.3.1.2 Reduction Catalyst. A 7.6-cm (3-in.) length of 6.4-mm (\1/
4\-in.) OD Inconel tubing fully packed with 100-mesh pure nickel
powder. The catalyst tube must be mounted vertically in a 400 deg.C
(750 deg.F) furnace.
6.3.1.3 Separation Column(s). A 30-cm (1-ft) length of 3.2-mm (\1/
8\-in.) OD stainless steel tubing packed with 60/80 mesh Unibeads 1S
followed by a 61-cm (2-ft) length of 3.2-mm (\1/8\-in.) OD stainless
steel tubing packed with 60/80 mesh Carbosieve G. The Carbosieve and
Unibeads columns must be baked separately at 200 deg.C (390 deg.F)
with carrier gas flowing through them for 24 hours before initial use.
6.3.1.4 Sample Injection System. A single 10-port GC sample
injection valve or a group of valves with sufficient ports fitted with
a sample loop properly sized to interface with the NMO analyzer (1-cc
loop recommended).
6.3.1.5 FID. An FID meeting the following specifications is
required:
6.3.1.5.1 Linearity. A linear response (5 percent)
over the operating range as demonstrated by the procedures established
in Section 10.1.2.3.
6.3.1.5.2 Range. A full scale range of 10 to 50,000 ppm
CH4. Signal attenuators shall be available to produce a
minimum signal response of 10 percent of full scale.
6.3.1.6 Data Recording System. Analog strip chart recorder or
digital integration system compatible with the FID for permanently
recording the analytical results.
6.3.2 Barometer. Mercury, aneroid, or other barometer capable of
measuring atmospheric pressure to within 1 mm Hg.
6.3.3 Temperature Sensor. Capable of measuring the laboratory
temperature within 1 deg.C (2 deg.F).
6.3.4 Vacuum Pump. Capable of evacuating to an absolute pressure
of 10 mm Hg.

7.0 Reagents and Standards

7.1 Sample Collection. The following reagents are required for
sample collection:
7.1.1 Dry Ice. Solid CO2, crushed.
7.1.2 Coarse Quartz Wool. 8 to 15 um.
7.1.3 Filters. Glass fiber filters, without organic binder.
7.2 NMO Analysis. The following gases are required for NMO
analysis:
7.2.1 Carrier Gases. Helium (He) and oxygen (O2)
containing less than 1 ppm CO2 and less than 0.1 ppm
hydrocarbon.
7.2.2 Fuel Gas. Hydrogen (H2), at least 99.999 percent
pure.
7.2.3 Combustion Gas. Either air (less than 0.1 ppm total
hydrocarbon content) or O2 (purity 99.99 percent or
greater), as required by the detector.
7.3 Condensate Analysis. The following are required for condensate
analysis:
7.3.1 Gases. Containing less than 1 ppm carbon.
7.3.1.1 Air.
7.3.1.2 Oxygen.
7.3.2 Liquids. To conform to the specifications established by the
Committee on Analytical Reagents of the American Chemical Society.
7.3.2.1 Hexane.
7.3.2.2 Decane.
7.4 Calibration. For all calibration gases, the manufacturer must
recommend a maximum shelf life for each cylinder (i.e., the length of
time the gas concentration is not expected to change more than
5 percent from its certified value). The date of gas
cylinder preparation, certified organic concentration, and recommended
maximum shelf life must be affixed to each cylinder before shipment
from the gas manufacturer to the buyer. The following calibration gases
are required:
7.4.1 Oxidation Catalyst Efficiency Check Calibration Gas. Gas
mixture standard with nominal concentration of 1 percent methane in
air.
7.4.2 FID Linearity and NMO Calibration Gases. Three gas mixture
standards with nominal propane concentrations of 20 ppm, 200 ppm, and
3000 ppm, in air.
7.4.3 CO2 Calibration Gases. Three gas mixture
standards with nominal CO2 concentrations of 50 ppm, 500
ppm, and 1 percent, in air.

Note:
Total NMO less than 1 ppm required for 1 percent mixture.

7.4.4 NMO Analyzer System Check Calibration Gases. Four
calibration gases are needed as follows:
7.4.4.1 Propane Mixture. Gas mixture standard containing (nominal)
50 ppm CO, 50 ppm CH4, 1 percent CO2, and 20 ppm
C3H8, prepared in air.
7.4.4.2 Hexane. Gas mixture standard containing (nominal) 50 ppm
hexane in air.
7.4.4.3 Toluene. Gas mixture standard containing (nominal) 20 ppm
toluene in air.
7.4.4.4 Methanol. Gas mixture standard containing (nominal) 100
ppm methanol in air.
7.5 Quality Assurance Audit Samples.
7.5.1 It is recommended, but not required, that a performance
audit sample be analyzed in conjunction with the field samples. The
audit sample should be in a suitable sample matrix at

[[Page 62047]]

a concentration similar to the actual field samples.
7.5.2 When making compliance determinations, and upon
availability, audit samples may be obtained from the appropriate EPA
Regional Office or from the responsible enforcement authority and
analyzed in conjunction with the field samples.

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

8.0 Sample Collection, Preservation, Transport, and Storage

8.1 Sampling Equipment Preparation.
8.1.1 Condensate Trap Cleaning. Before its initial use and after
each use, a condensate trap should be thoroughly cleaned and checked to
ensure that it is not contaminated. Both cleaning and checking can be
accomplished by installing the trap in the condensate recovery system
and treating it as if it were a sample. The trap should be heated as
described in Section 11.1.3. A trap may be considered clean when the
CO2 concentration in its effluent gas drops below 10 ppm.
This check is optional for traps that most recently have been used to
collect samples which were then recovered according to the procedure in
Section 11.1.3.
8.1.2 Sample Tank Evacuation and Leak-Check. Evacuate the sample
tank to 10 mm Hg absolute pressure or less. Then close the sample tank
valve, and allow the tank to sit for 60 minutes. The tank is acceptable
if a change in tank vacuum of less than 1 mm Hg is noted. The
evacuation and leak-check may be conducted either in the laboratory or
the field.
8.1.3 Sampling Train Assembly. Just before assembly, measure the
tank vacuum using a mercury manometer. Record this vacuum, the ambient
temperature, and the barometric pressure at this time. Close the sample
tank valve and assemble the sampling system as shown in Figure 25-1.
Immerse the condensate trap body in dry ice at least 30 minutes before
commencing sampling to improve collection efficiency. The point where
the inlet tube joins the trap body should be 2.5 to 5 cm (1 to 2 in.)
above the top of the dry ice.
8.1.4 Pretest Leak-Check. A pretest leak-check is required.
Calculate or measure the approximate volume of the sampling train from
the probe tip to the sample tank valve. After assembling the sampling
train, plug the probe tip, and make certain that the sample tank valve
is closed. Turn on the vacuum pump, and evacuate the sampling system
from the probe tip to the sample tank valve to an absolute pressure of
10 mm Hg or less. Close the purge valve, turn off the pump, wait a
minimum period of 10 minutes, and recheck the indicated vacuum.
Calculate the maximum allowable pressure change based on a leak rate of
1 percent of the sampling rate using Equation 25-1, Section 12.2. If
the measured pressure change exceeds the allowable, correct the problem
and repeat the leak-check before beginning sampling.
8.2 Sample Collection.
8.2.1 Unplug the probe tip, and place the probe into the stack
such that the probe is perpendicular to the duct or stack axis; locate
the probe tip at a single preselected point of average velocity facing
away from the direction of gas flow. For stacks having a negative
static pressure, seal the sample port sufficiently to prevent air in-
leakage around the probe. Set the probe temperature controller to 129
deg.C (265 deg.F) and the filter temperature controller to 121 deg.C
(250 deg.F). Allow the probe and filter to heat for about 30 minutes
before purging the sample train.
8.2.2 Close the sample valve, open the purge valve, and start the
vacuum pump. Set the flow rate between 60 and 100 cm3/min
(0.13 and 0.21 ft3/hr), and purge the train with stack gas
for at least 10 minutes.
8.2.3 When the temperatures at the exit ends of the probe and
filter are within the corresponding specified ranges, check the dry ice
level around the condensate trap, and add dry ice if necessary. Record
the clock time. To begin sampling, close the purge valve and stop the
pump. Open the sample valve and the sample tank valve. Using the flow
control valve, set the flow through the sample train to the proper
rate. Adjust the flow rate as necessary to maintain a constant rate
(10 percent) throughout the duration of the sampling
period. Record the sample tank vacuum and flowmeter setting at 5-minute
intervals. (See Figure 25-8.) Select a total sample time greater than
or equal to the minimum sampling time specified in the applicable
subpart of the regulations; end the sampling when this time period is
reached or when a constant flow rate can no longer be maintained
because of reduced sample tank vacuum.

Note: If sampling had to be stopped before obtaining the minimum
sampling time (specified in the applicable subpart) because a
constant flow rate could not be maintained, proceed as follows:
After closing the sample tank valve, remove the used sample tank
from the sampling train (without disconnecting other portions of the
sampling train). Take another evacuated and leak-checked sample
tank, measure and record the tank vacuum, and attach the new tank to
the sampling train. After the new tank is attached to the sample
train, proceed with the sampling until the required minimum sampling
time has been exceeded.

8.3 Sample Recovery. After sampling is completed, close the flow
control valve, and record the final tank vacuum; then record the tank
temperature and barometric pressure. Close the sample tank valve, and
disconnect the sample tank from the sample system. Disconnect the
condensate trap at the inlet to the rate meter, and tightly seal both
ends of the condensate trap. Do not include the probe from the stack to
the filter as part of the condensate sample.
8.4 Sample Storage and Transport. Keep the trap packed in dry ice
until the samples are returned to the laboratory for analysis. Ensure
that run numbers are identified on the condensate trap and the sample
tank(s).

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.1.1........................ Initial Ensure acceptable
performance condensate recovery
check of efficiency.
condensate
recovery
apparatus.
10.1.2, 10.2.................. NMO analyzer Ensure precision of
initial and analytical results.
daily
performance
checks.
11.3.......................... Audit Sample Evaluate analytical
Analyses. technique and
instrument
calibration.
------------------------------------------------------------------------

10.0 Calibration and Standardization

Note: Maintain a record of performance of each item.

10.1 Initial Performance Checks.
10.1.1 Condensate Recovery Apparatus. Perform these tests before
the system is first placed in operation, after any shutdown of 6 months
or more, and after any major modification of the system, or at the
frequency recommended by the manufacturer.

[[Page 62048]]

10.1.1.1 Carrier Gas and Auxiliary O2 Blank Check.
Analyze each new tank of carrier gas or auxiliary O2 with
the NMO analyzer to check for contamination. Treat the gas cylinders as
noncondensible gas samples, and analyze according to the procedure in
Section 11.2.3. Add together any measured CH4, CO,
CO2, or NMO. The total concentration must be less than 5
ppm.
10.1.1.2 Oxidation Catalyst Efficiency Check.
10.1.1.2.1 With a clean condensate trap installed in the recovery
system or a \1/8\" stainless steel connector tube, replace the carrier
gas cylinder with the high level methane standard gas cylinder (Section
7.4.1). Set the four-port valve to the recovery position, and attach an
ICV to the recovery system. With the sample recovery valve in vent
position and the flow-control and ICV valves fully open, evacuate the
manometer or gauge, the connecting tubing, and the ICV to 10 mm Hg
absolute pressure. Close the flow-control and vacuum pump valves.
10.1.1.2.2 After the NDIR response has stabilized, switch the
sample recovery valve from vent to collect. When the manometer or
pressure gauge begins to register a slight positive pressure, open the
flow-control valve. Keep the flow adjusted such that the pressure in
the system is maintained within 10 percent of atmospheric pressure.
Continue collecting the sample in a normal manner until the ICV is
filled to a nominal gauge pressure of 300 mm Hg. Close the ICV valve,
and remove the ICV from the system. Place the sample recovery valve in
the vent position, and return the recovery system to its normal carrier
gas and normal operating conditions. Analyze the ICV for CO2
using the NMO analyzer; the catalyst efficiency is acceptable if the
CO2 concentration is within 2 percent of the methane
standard concentration.
10.1.1.3 System Performance Check. Construct a liquid sample
injection unit similar in design to the unit shown in Figure 25-7.
Insert this unit into the condensate recovery and conditioning system
in place of a condensate trap, and set the carrier gas and auxiliary
O2 flow rates to normal operating levels. Attach an
evacuated ICV to the system, and switch from system vent to collect.
With the carrier gas routed through the injection unit and the
oxidation catalyst, inject a liquid sample (see Sections 10.1.1.3.1 to
10.1.1.3.4) into the injection port. Operate the trap recovery system
as described in Section 11.1.3. Measure the final ICV pressure, and
then analyze the vessel to determine the CO2 concentration.
For each injection, calculate the percent recovery according to Section
12.7. Calculate the relative standard deviation for each set of
triplicate injections according to Section 12.8. The performance test
is acceptable if the average percent recovery is 100 5
percent and the relative standard deviation is less than 2 percent for
each set of triplicate injections.
10.1.1.3.1 50 l hexane.
10.1.1.3.2 10 l hexane.
10.1.1.3.3 50 l decane.
10.1.1.3.4 10 l decane.
10.1.2 NMO Analyzer. Perform these tests before the system is
first placed in operation, after any shutdown longer than 6 months, and
after any major modification of the system.
10.1.2.1 Oxidation Catalyst Efficiency Check. Turn off or bypass
the NMO analyzer reduction catalyst. Make triplicate injections of the
high level methane standard (Section 7.4.1). The oxidation catalyst
operation is acceptable if the FID response is less than 1 percent of
the injected methane concentration.
10.1.2.2 Reduction Catalyst Efficiency Check. With the oxidation
catalyst unheated or bypassed and the heated reduction catalyst
bypassed, make triplicate injections of the high level methane standard
(Section 7.4.1). Repeat this procedure with both catalysts operative.
The reduction catalyst operation is acceptable if the responses under
both conditions agree within 5 percent of their average.
10.1.2.3 NMO Analyzer Linearity Check Calibration. While operating
both the oxidation and reduction catalysts, conduct a linearity check
of the analyzer using the propane standards specified in Section 7.4.2.
Make triplicate injections of each calibration gas. For each gas (i.e.,
each set of triplicate injections), calculate the average response
factor (area/ppm C) for each gas, as well as and the relative standard
deviation (according to Section 12.8). Then calculate the overall mean
of the response factor values. The instrument linearity is acceptable
if the average response factor of each calibration gas is within 2.5
percent of the overall mean value and if the relative standard
deviation gas is less than 2 percent of the overall mean value. Record
the overall mean of the propane response factor values as the NMO
calibration response factor (RFNMO). Repeat the linearity
check using the CO2 standards specified in Section 7.4.3.
Make triplicate injections of each gas, and then calculate the average
response factor (area/ppm C) for each gas, as well as the overall mean
of the response factor values. Record the overall mean of the response
factor values as the CO2 calibration response factor
(RFCO2). The RFCO2 must be within 10 percent of
the RFNMO.
10.1.2.4 System Performance Check. Check the column separation and
overall performance of the analyzer by making triplicate injections of
the calibration gases listed in Section 7.4.4. The analyzer performance
is acceptable if the measured NMO value for each gas (average of
triplicate injections) is within 5 percent of the expected value.
10.2 NMO Analyzer Daily Calibration. The following calibration
procedures shall be performed before and immediately after the analysis
of each set of samples, or on a daily basis, whichever is more
stringent:
10.2.1 CO2 Response Factor. Inject triplicate samples
of the high level CO2 calibration gas (Section 7.4.3), and
calculate the average response factor. The system operation is adequate
if the calculated response factor is within 5 percent of the
RFCO2 calculated during the initial performance test
(Section 10.1.2.3). Use the daily response factor (DRFCO2)
for analyzer calibration and the calculation of measured CO2
concentrations in the ICV samples.
10.2.2 NMO Response Factors. Inject triplicate samples of the
mixed propane calibration cylinder gas (Section 7.4.4.1), and calculate
the average NMO response factor. The system operation is adequate if
the calculated response factor is within 10 percent of the
RFNMO calculated during the initial performance test
(Section 10.1.2.4). Use the daily response factor (DRFNMO)
for analyzer calibration and calculation of NMO concentrations in the
sample tanks.
10.3 Sample Tank and ICV Volume. The volume of the gas sampling
tanks used must be determined. Determine the tank and ICV volumes by
weighing them empty and then filled with deionized distilled water;
weigh to the nearest 5 g, and record the results. Alternatively,
measure the volume of water used to fill them to the nearest 5 ml.

11.0 Analytical Procedure

11.1 Condensate Recovery. See Figure 25-9. Set the carrier gas
flow rate, and heat the catalyst to its operating temperature to
condition the apparatus.
11.1.1 Daily Performance Checks. Each day before analyzing any
samples, perform the following tests:
11.1.1.1 Leak-Check. With the carrier gas inlets and the sample
recovery valve closed, install a clean condensate trap in the system,
and evacuate the system to 10 mm Hg absolute pressure or less. Monitor
the system pressure for 10 minutes. The

[[Page 62049]]

system is acceptable if the pressure change is less than 2 mm Hg.
11.1.1.2 System Background Test. Adjust the carrier gas and
auxiliary oxygen flow rate to their normal values of 100 cc/min and 150
cc/min, respectively, with the sample recovery valve in vent position.
Using a 10-ml syringe, withdraw a sample from the system effluent
through the syringe port. Inject this sample into the NMO analyzer, and
measure the CO2 content. The system background is acceptable
if the CO2 concentration is less than 10 ppm.
11.1.1.3 Oxidation Catalyst Efficiency Check. Conduct a catalyst
efficiency test as specified in Section 10.1.1.2. If the criterion of
this test cannot be met, make the necessary repairs to the system
before proceeding.
11.1.2 Condensate Trap CO2 Purge and Sample Tank
Pressurization.
11.1.2.1 After sampling is completed, the condensate trap will
contain condensed water and organics and a small volume of sampled gas.
This gas from the stack may contain a significant amount of
CO2 which must be removed from the condensate trap before
the sample is recovered. This is accomplished by purging the condensate
trap with zero air and collecting the purged gas in the original sample
tank.
11.1.2.2 Begin with the sample tank and condensate trap from the
test run to be analyzed. Set the four-port valve of the condensate
recovery system in the CO2 purge position as shown in Figure
25-9. With the sample tank valve closed, attach the sample tank to the
sample recovery system. With the sample recovery valve in the vent
position and the flow control valve fully open, evacuate the manometer
or pressure gauge to the vacuum of the sample tank. Next, close the
vacuum pump valve, open the sample tank valve, and record the tank
pressure.
11.1.2.3 Attach the dry ice-cooled condensate trap to the recovery
system, and initiate the purge by switching the sample recovery valve
from vent to collect position. Adjust the flow control valve to
maintain atmospheric pressure in the recovery system. Continue the
purge until the CO2 concentration of the trap effluent is
less than 5 ppm. CO2 concentration in the trap effluent
should be measured by extracting syringe samples from the recovery
system and analyzing the samples with the NMO analyzer. This procedure
should be used only after the NDIR response has reached a minimum
level. Using a 10-ml syringe, extract a sample from the syringe port
prior to the NDIR, and inject this sample into the NMO analyzer.
11.1.2.4 After the completion of the CO2 purge, use the
carrier gas bypass valve to pressurize the sample tank to approximately
1,060 mm Hg absolute pressure with zero air.
11.1.3 Recovery of the Condensate Trap Sample (See Figure 25-10).
11.1.3.1 Attach the ICV to the sample recovery system. With the
sample recovery valve in a closed position, between vent and collect,
and the flow control and ICV valves fully open, evacuate the manometer
or gauge, the connecting tubing, and the ICV to 10 mm Hg absolute
pressure. Close the flow-control and vacuum pump valves.
11.1.3.2 Begin auxiliary oxygen flow to the oxidation catalyst at
a rate of 150 cc/min, then switch the four-way valve to the trap
recovery position and the sample recovery valve to collect position.
The system should now be set up to operate as indicated in Figure 25-
10. After the manometer or pressure gauge begins to register a slight
positive pressure, open the flow control valve. Adjust the flow-control
valve to maintain atmospheric pressure in the system within 10 percent.
11.1.3.3 Remove the condensate trap from the dry ice, and allow it
to warm to ambient temperature while monitoring the NDIR response. If,
after 5 minutes, the CO2 concentration of the catalyst
effluent is below 10,000 ppm, discontinue the auxiliary oxygen flow to
the oxidation catalyst. Begin heating the trap by placing it in a
furnace preheated to 200 deg.C (390 deg.F). Once heating has begun,
carefully monitor the NDIR response to ensure that the catalyst
effluent concentration does not exceed 50,000 ppm. Whenever the
CO2 concentration exceeds 50,000 ppm, supply auxiliary
oxygen to the catalyst at the rate of 150 cc/min. Begin heating the
tubing that connected the heated sample box to the condensate trap only
after the CO2 concentration falls below 10,000 ppm. This
tubing may be heated in the same oven as the condensate trap or with an
auxiliary heat source such as a heat gun. Heating temperature must not
exceed 200 deg.C (390 deg.F). If a heat gun is used, heat the tubing
slowly along its entire length from the upstream end to the downstream
end, and repeat the pattern for a total of three times. Continue the
recovery until the CO2 concentration drops to less than 10
ppm as determined by syringe injection as described under the
condensate trap CO2 purge procedure (Section 11.1.2).
11.1.3.4 After the sample recovery is completed, use the carrier
gas bypass valve to pressurize the ICV to approximately 1060 mm Hg
absolute pressure with zero air.
11.2 Analysis. Once the initial performance test of the NMO
analyzer has been successfully completed (see Section 10.1.2) and the
daily CO2 and NMO response factors have been determined (see
Section 10.2), proceed with sample analysis as follows:
11.2.1 Operating Conditions. The carrier gas flow rate is 29.5 cc/
min He and 2.2 cc/min O2. The column oven is heated to 85
deg.C (185 deg.F). The order of elution for the sample from the column
is CO, CH4, CO2, and NMO.
11.2.2 Analysis of Recovered Condensate Sample. Purge the sample
loop with sample, and then inject the sample. Under the specified
operating conditions, the CO2 in the sample will elute in
approximately 100 seconds. As soon as the detector response returns to
baseline following the CO2 peak, switch the carrier gas flow
to backflush, and raise the column oven temperature to 195 deg.C (380
deg.F) as rapidly as possible. A rate of 30 deg.C/min (90 deg.F) has
been shown to be adequate. Record the value obtained for the
condensible organic material (Ccm) measured as
CO2 and any measured NMO. Return the column oven temperature
to 85 deg.C (185 deg.F) in preparation for the next analysis. Analyze
each sample in triplicate, and report the average Ccm.
11.2.3 Analysis of Sample Tank. Perform the analysis as described
in Section 11.2.2, but record only the value measured for NMO
(Ctm).
11.3 Audit Sample Analysis.
11.3.1 When the method is used to analyze samples to demonstrate
compliance with a source emission regulation, an audit sample, if
available, must be analyzed.
11.3.2 Concurrently analyze the audit sample and the compliance
samples in the same manner to evaluate the technique of the analyst and
the standards preparation.
11.3.3 The same analyst, analytical reagents, and analytical
system must be used for the compliance samples and the audit sample. If
this condition is met, duplicate auditing of subsequent compliance
analyses for the same enforcement agency within a 30-day period is
waived. An audit sample set may not be used to validate different sets
of compliance samples under the jurisdiction of separate enforcement
agencies, unless prior arrangements have been made with both
enforcement agencies.
11.4 Audit Sample Results.
11.4.1 Calculate the audit sample concentrations and submit
results using the instructions provided with the audit samples.

[[Page 62050]]

11.4.2 Report the results of the audit samples and the compliance
determination samples along with their identification numbers, and the
analyst's name to the responsible enforcement authority. Include this
information with reports of any subsequent compliance analyses for the
same enforcement authority during the 30-day period.
11.4.3 The concentrations of the audit samples obtained by the
analyst must agree within 20 percent of the actual concentration. If
the 20-percent specification is not met, reanalyze the compliance and
audit samples, and include initial and reanalysis values in the test
report.
11.4.4 Failure to meet the 20-percent specification may require
retests until the audit problems are resolved. However, if the audit
results do not affect the compliance or noncompliance status of the
affected facility, the Administrator may waive the reanalysis
requirement, further audits, or retests and accept the results of the
compliance test. While steps are being taken to resolve audit analysis
problems, the Administrator may also choose to use the data to
determine the compliance or noncompliance status of the affected
facility.

12.0 Data Analysis and Calculations

Carry out the calculations, retaining at least one extra
significant figure beyond that of the acquired data. Round off figures
after final calculations. All equations are written using absolute
pressure; absolute pressures are determined by adding the measured
barometric pressure to the measured gauge or manometer pressure.
12.1 Nomenclature.

C = TGNMO concentration of the effluent, ppm C equivalent.
Cc = Calculated condensible organic (condensate trap)
concentration of the effluent, ppm C equivalent.
Ccm = Measured concentration (NMO analyzer) for the
condensate trap ICV, ppm CO2.
Ct = Calculated noncondensible organic concentration (sample
tank) of the effluent, ppm C equivalent.
Ctm = Measured concentration (NMO analyzer) for the sample
tank, ppm NMO.
F = Sampling flow rate, cc/min.
L = Volume of liquid injected, l.
M = Molecular weight of the liquid injected, g/g-mole.
Mc = TGNMO mass concentration of the effluent, mg C/dsm\3\.
N = Carbon number of the liquid compound injected (N = 12 for decane, N
= 6 for hexane).
n = Number of data points.
Pf = Final pressure of the intermediate collection vessel,
mm Hg absolute.
Pb = Barometric pressure, cm Hg.
Pti = Gas sample tank pressure before sampling, mm Hg
absolute.
Pt = Gas sample tank pressure after sampling, but before
pressurizing, mm Hg absolute.
Ptf = Final gas sample tank pressure after pressurizing, mm
Hg absolute.
q = Total number of analyzer injections of intermediate collection
vessel during analysis (where k = injection number, 1 * * * q).
r = Total number of analyzer injections of sample tank during analysis
(where j = injection number,
1 * * * r).
r = Density of liquid injected, g/cc.
Tf = Final temperature of intermediate collection vessel,
deg.K.
Tti = Sample tank temperature before sampling, deg.K.
Tt = Sample tank temperature at completion of sampling,
deg.K.
Ttf = Sample tank temperature after pressurizing, deg.K.
V = Sample tank volume, m\3\.
Vt = Sample train volume, cc.
Vv = Intermediate collection vessel volume, m\3\.
Vs = Gas volume sampled, dsm\3\.
xi = Individual measurements.
x= Mean value.
P = Allowable pressure change, cm Hg.
= Leak-check period, min.

12.2 Allowable Pressure Change. For the pretest leak-check,
calculate the allowable pressure change using Equation 25-1:
[GRAPHIC] [TIFF OMITTED] TR17OC00.364

12.3 Sample Volume. For each test run, calculate the gas volume
sampled using Equation 25-2:
[GRAPHIC] [TIFF OMITTED] TR17OC00.365

12.4 Noncondensible Organics. For each sample tank, determine the
concentration of nonmethane organics (ppm C) using Equation 25-3:
[GRAPHIC] [TIFF OMITTED] TR17OC00.366

12.5 Condensible Organics. For each condensate trap determine the
concentration of organics (ppm C) using Equation 25-4:
[GRAPHIC] [TIFF OMITTED] TR17OC00.367

12.6 TGNMO Mass Concentration. Determine the TGNMO mass
concentration as carbon for each test run, using Equation 25-5:
[GRAPHIC] [TIFF OMITTED] TR17OC00.368

12.7 Percent Recovery. Calculate the percent recovery for the
liquid injections to the condensate recovery and conditioning system
using Equation 25-6:
[GRAPHIC] [TIFF OMITTED] TR17OC00.369

where K = 1.604 ( deg.K)(g-mole)(%)/(mm Hg)(ml)(m\3\)(ppm).
12.8 Relative Standard Deviation. Use Equation 25-7 to calculate
the relative standard deviation (RSD) of percent recovery and analyzer
linearity.

[[Page 62051]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.370

13.0 Method Performance

13.1 Range. The minimum detectable limit of the method has been
determined to be 50 parts per million by volume (ppm). No upper limit
has been established.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Salo, A.E., S. Witz, and R.D. MacPhee. Determination of Solvent
Vapor Concentrations by Total Combustion Analysis: A Comparison of
Infrared with Flame Ionization Detectors. Paper No. 75-33.2. (Presented
at the 68th Annual Meeting of the Air Pollution Control Association.
Boston, MA. June 15-20, 1975.) 14 p.
2. Salo, A.E., W.L. Oaks, and R.D. MacPhee. Measuring the Organic
Carbon Content of Source Emissions for Air Pollution Control. Paper No.
74-190. (Presented at the 67th Annual Meeting of the Air Pollution
Control Association. Denver, CO. June 9-13, 1974.) 25 p.
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[[Page 62052]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.371

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[GRAPHIC] [TIFF OMITTED] TR17OC00.380

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[[Page 62062]]

Method 25A--Determination of Total Gaseous Organic Concentration
Using a Flame Ionization Analyzer

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Total Organic Compounds........ N/A 2% of span.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of total gaseous organic concentration of vapors consisting primarily
of alkanes, alkenes, and/or arenes (aromatic hydrocarbons). The
concentration is expressed in terms of propane (or other appropriate
organic calibration gas) or in terms of carbon.
1.3 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 source through a heated
sample line and glass fiber filter to a flame ionization analyzer
(FIA). Results are reported as volume concentration equivalents of the
calibration gas or as carbon equivalents.

3.0 Definitions

3.1 Calibration drift means the difference in the measurement
system response to a mid-level calibration gas before and after a
stated period of operation during which no unscheduled maintenance,
repair, or adjustment took place.
3.2 Calibration error means the difference between the gas
concentration indicated by the measurement system and the know
concentration of the calibration gas.
3.3 Calibration gas means a known concentration of a gas in an
appropriate diluent gas.
3.4 Measurement system means the total equipment required for the
determination of the gas concentration. The system consists of the
following major subsystems:
3.4.1 Sample interface means that portion of a system used for one
or more of the following: sample acquisition, sample transportation,
sample conditioning, or protection of the analyzer(s) from the effects
of the stack effluent.
3.4.2 Organic analyzer means that portion of the measurement
system that senses the gas to be measured and generates an output
proportional to its concentration.
3.5 Response time means the time interval from a step change in
pollutant concentration at the inlet to the emission measurement system
to the time at which 95 percent of the corresponding final value is
reached as displayed on the recorder.
3.6 Span Value means the upper limit of a gas concentration
measurement range that is specified for affected source categories in
the applicable part of the regulations. The span value is established
in the applicable regulation and is usually 1.5 to 2.5 times the
applicable emission limit. If no span value is provided, use a span
value equivalent to 1.5 to 2.5 times the expected concentration. For
convenience, the span value should correspond to 100 percent of the
recorder scale.
3.7 Zero drift means the difference in the measurement system
response to a zero level calibration gas before or after a stated
period of operation during which no unscheduled maintenance, repair, or
adjustment took place.

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

6.1 Measurement System. Any measurement system for total organic
concentration that meets the specifications of this method. A schematic
of an acceptable measurement system is shown in Figure 25A-1. All
sampling components leading to the analyzer shall be heated
110 deg.C (220 deg.F) throughout the sampling period, unless safety
reasons are cited (Section 5.2) The essential components of the
measurement system are described below:
6.1.1 Organic Concentration Analyzer. A flame ionization analyzer
(FIA) capable of meeting or exceeding the specifications of this
method. The flame ionization detector block shall be heated >120 deg.C
(250 deg.F).
6.1.2 Sample Probe. Stainless steel, or equivalent, three-hole
rake type. Sample holes shall be 4 mm (0.16-in.) in diameter or smaller
and located at 16.7, 50, and 83.3 percent of the equivalent stack
diameter. Alternatively, a single opening probe may be used so that a
gas sample is collected from the centrally located 10 percent area of
the stack cross-section.
6.1.3 Heated Sample Line. Stainless steel or Teflon'' tubing to
transport the sample gas to the analyzer. The sample line should be
heated (110 deg.C) to prevent any condensation.
6.1.4 Calibration Valve Assembly. A three-way valve assembly to
direct the zero and calibration gases to the analyzers is recommended.
Other methods, such as quick-connect lines, to route calibration gas to
the analyzers are applicable.
6.1.5 Particulate Filter. An in-stack or an out-of-stack glass
fiber filter is recommended if exhaust gas particulate loading is
significant. An out-of-stack filter should be heated to prevent any
condensation.
6.1.6 Recorder. A strip-chart recorder, analog computer, or
digital recorder for recording measurement data. The minimum data
recording requirement is one measurement value per minute.

7.0 Reagents and Standards

7.1 Calibration Gases. The calibration gases for the gas analyzer
shall be propane in air or propane in nitrogen. Alternatively, organic
compounds other than propane can be used; the appropriate corrections
for response factor must be made. Calibration gases shall be prepared
in accordance with the procedure listed in Citation 2 of Section 16.
Additionally, the manufacturer of the cylinder should provide a
recommended shelf life for each calibration gas cylinder over which the
concentration does not change more than 2 percent from the
certified

[[Page 62063]]

value. For calibration gas values not generally available (i.e.,
organics between 1 and 10 percent by volume), alternative methods for
preparing calibration gas mixtures, such as dilution systems (Test
Method 205, 40 CFR Part 51, Appendix M), may be used with prior
approval of the Administrator.
7.1.1 Fuel. A 40 percent H2/60 percent N2
gas mixture is recommended to avoid an oxygen synergism effect that
reportedly occurs when oxygen concentration varies significantly from a
mean value.
7.1.2 Zero Gas. High purity air with less than 0.1 part per
million by volume (ppmv) of organic material (propane or carbon
equivalent) or less than 0.1 percent of the span value, whichever is
greater.
7.1.3 Low-level Calibration Gas. An organic calibration gas with a
concentration equivalent to 25 to 35 percent of the applicable span
value.
7.1.4 Mid-level Calibration Gas. An organic calibration gas with a
concentration equivalent to 45 to 55 percent of the applicable span
value.
7.1.5 High-level Calibration Gas. An organic calibration gas with
a concentration equivalent to 80 to 90 percent of the applicable span
value.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Selection of Sampling Site. The location of the sampling site
is generally specified by the applicable regulation or purpose of the
test (i.e., exhaust stack, inlet line, etc.). The sample port shall be
located to meet the testing requirements of Method 1.
8.2 Location of Sample Probe. Install the sample probe so that the
probe is centrally located in the stack, pipe, or duct and is sealed
tightly at the stack port connection.
8.3 Measurement System Preparation. Prior to the emission test,
assemble the measurement system by following the manufacturer's written
instructions for preparing sample interface and the organic analyzer.
Make the system operable (Section 10.1).
8.4 Calibration Error Test. Immediately prior to the test series
(within 2 hours of the start of the test), introduce zero gas and high-
level calibration gas at the calibration valve assembly. Adjust the
analyzer output to the appropriate levels, if necessary. Calculate the
predicted response for the low-level and mid-level gases based on a
linear response line between the zero and high-level response. Then
introduce low-level and mid-level calibration gases successively to the
measurement system. Record the analyzer responses for low-level and
mid-level calibration gases and determine the differences between the
measurement system responses and the predicted responses. These
differences must be less than 5 percent of the respective calibration
gas value. If not, the measurement system is not acceptable and must be
replaced or repaired prior to testing. No adjustments to the
measurement system shall be conducted after the calibration and before
the drift check (Section 8.6.2). If adjustments are necessary before
the completion of the test series, perform the drift checks prior to
the required adjustments and repeat the calibration following the
adjustments. If multiple electronic ranges are to be used, each
additional range must be checked with a mid-level calibration gas to
verify the multiplication factor.
8.5 Response Time Test. Introduce zero gas into the measurement
system at the calibration valve assembly. When the system output has
stabilized, switch quickly to the high-level calibration gas. Record
the time from the concentration change to the measurement system
response equivalent to 95 percent of the step change. Repeat the test
three times and average the results.
8.6 Emission Measurement Test Procedure.
8.6.1 Organic Measurement. Begin sampling at the start of the test
period, recording time and any required process information as
appropriate. In particulate, note on the recording chart, periods of
process interruption or cyclic operation.
8.6.2 Drift Determination. Immediately following the completion of
the test period and hourly during the test period, reintroduce the zero
and mid-level calibration gases, one at a time, to the measurement
system at the calibration valve assembly. (Make no adjustments to the
measurement system until both the zero and calibration drift checks are
made.) Record the analyzer response. If the drift values exceed the
specified limits, invalidate the test results preceding the check and
repeat the test following corrections to the measurement system.
Alternatively, recalibrate the test measurement system as in Section
8.4 and report the results using both sets of calibration data (i.e.,
data determined prior to the test period and data determined following
the test period).

Note: Note on the recording chart periods of process
interruption or cyclic operation.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Method section measure Effect
------------------------------------------------------------------------
8.4........................... Zero and Ensures that bias
calibration introduced by drift
drift tests. in the measurement
system output during
the run is no
greater than 3
percent of span.
------------------------------------------------------------------------

10.0 Calibration and Standardization

10.1 FIA equipment can be calibrated for almost any range of total
organic concentrations. For high concentrations of organics (> 1.0
percent by volume as propane), modifications to most commonly available
analyzers are necessary. One accepted method of equipment modification
is to decrease the size of the sample to the analyzer through the use
of a smaller diameter sample capillary. Direct and continuous
measurement of organic concentration is a necessary consideration when
determining any modification design.

11.0 Analytical Procedure

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

12.0 Calculations and Data Analysis

12.1 Determine the average organic concentration in terms of ppmv
as propane or other calibration gas. The average shall be determined by
integration of the output recording over the period specified in the
applicable regulation. If results are required in terms of ppmv as
carbon, adjust measured concentrations using Equation 25A-1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.381

Where:
Cc = Organic concentration as carbon, ppmv.
Cmeas = Organic concentration as measured, ppmv.
K = Carbon equivalent correction factor.
= 2 for ethane.
= 3 for propane.
= 4 for butane.
= Appropriate response factor for other organic calibration gases.

[[Page 62064]]

13.0 Method Performance

13.1 Measurement System Performance Specifications.
13.1.1 Zero Drift. Less than 3 percent of the span
value.
13.1.2 Calibration Drift. Less than 3 percent of span
value.
13.1.3 Calibration Error. Less than 5 percent of the
calibration gas value.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Measurement of Volatile Organic Compounds--Guideline Series.
U.S. Environmental Protection Agency. Research Triangle Park, NC.
Publication No. EPA-450/2-78-041. June 1978. p. 46-54.
2. EPA Traceability Protocol for Assay and Certification of
Gaseous Calibration Standards. U.S. Environmental Protection Agency,
Quality Assurance and Technical Support Division. Research Triangle
Park, N.C. September 1993.
3. Gasoline Vapor Emission Laboratory Evaluation--Part 2. U.S.
Environmental Protection Agency, Office of Air Quality Planning and
Standards. Research Triangle Park, NC. EMB Report No. 75-GAS-6.
August 1975.
BILLING CODE 6560--50--P

[[Page 62065]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.382

BILLING CODE 6560--50--C

[[Page 62066]]

Method 25B--Determination of Total Gaseous Organic Concentration
Using a Nondispersive Infrared Analyzer

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling) 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 6C, and Method 25A.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Total Organic Compounds........... N/A 2% of span.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of total gaseous organic concentration of vapors consisting primarily
of alkanes. Other organic materials may be measured using the general
procedure in this method, the appropriate calibration gas, and an
analyzer set to the appropriate absorption band.
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

A gas sample is extracted from the source through a heated sample
line, if necessary, and glass fiber filter to a nondispersive infrared
analyzer (NDIR). Results are reported as volume concentration
equivalents of the calibration gas or as carbon equivalents.

3.0 Definitions

Same as Method 25A, Section 3.0.

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

Same as Method 25A, Section 6.0, with the exception of the
following:
6.1 Organic Concentration Analyzer. A nondispersive infrared
analyzer designed to measure alkane organics and capable of meeting or
exceeding the specifications in this method.

7.0 Reagents and Standards

Same as Method 25A, Section 7.1. No fuel gas is required for an
NDIR.

8.0 Sample Collection, Preservation, Storage, and Transport

Same as Method 25A, Section 8.0.

9.0 Quality Control

Same as Method 25A, Section 9.0.

10.0 Calibration and Standardization

Same as Method 25A, Section 10.0.

11.0 Analytical Procedure

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

12.0 Calculations and Data Analysis

Same as Method 25A, Section 12.0.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as Method 25A, Section 16.0.

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

Method 25C--Determination of Nonmethane Organic Compounds (NMOC) in
Landfill Gases

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 also have a thorough knowledge of EPA Method 25.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Nonmethane organic compounds (NMOC)....... No CAS number assigned.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable to the sampling and
measurement of NMOC as carbon in landfill gases (LFG).
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 sample probe that has been perforated at one end is driven
or augured to a depth of 0.9 m (3 ft) below the bottom of the landfill
cover. A sample of the landfill gas is extracted with an evacuated
cylinder. The NMOC content of the gas is determined by injecting a
portion of the gas into a gas chromatographic column to separate the
NMOC from carbon monoxide (CO), carbon dioxide (CO2), and
methane (CH4); the NMOC are oxidized to CO2,
reduced to CH4, and measured by a flame ionization detector
(FID). In this manner, the variable response of the FID associated with
different types of organics is eliminated.

3.0 Definitions. [Reserved]

4.0 Interferences. [Reserved]

5.0 Safety

5.1 Since this method is complex, only experienced personnel
should perform this test. LFG contains methane, therefore explosive
mixtures may exist on or near the landfill. It is advisable to take
appropriate safety precautions when testing landfills, such as
refraining from smoking and installing explosion-proof equipment.

6.0 Equipment and Supplies

6.1 Sample Probe. Stainless steel, with the bottom third
perforated. The sample probe must be capped at the bottom and must have
a threaded cap with a sampling attachment at the top.

[[Page 62067]]

The sample probe must be long enough to go through and extend no less
than 0.9 m (3 ft) below the landfill cover. If the sample probe is to
be driven into the landfill, the bottom cap should be designed to
facilitate driving the probe into the landfill.
6.2 Sampling Train.
6.2.1 Rotameter with Flow Control Valve. Capable of measuring a
sample flow rate of 100 10 ml/min. The control valve must
be made of stainless steel.
6.2.2 Sampling Valve. Stainless steel.
6.2.3 Pressure Gauge. U-tube mercury manometer, or equivalent,
capable of measuring pressure to within 1 mm Hg (0.5 in H2O)
in the range of 0 to 1,100 mm Hg (0 to 590 in H2O).
6.2.4 Sample Tank. Stainless steel or aluminum cylinder, equipped
with a stainless steel sample tank valve.
6.3 Vacuum Pump. Capable of evacuating to an absolute pressure of
10 mm Hg (5.4 in H2O).
6.4 Purging Pump. Portable, explosion proof, and suitable for
sampling NMOC.
6.5 Pilot Probe Procedure. The following are needed only if the
tester chooses to use the procedure described in Section 8.2.1.
6.5.1 Pilot Probe. Tubing of sufficient strength to withstand
being driven into the landfill by a post driver and an outside diameter
of at least 6 mm (0.25 in.) smaller than the sample probe. The pilot
probe shall be capped on both ends and long enough to go through the
landfill cover and extend no less than 0.9 m (3 ft) into the landfill.
6.5.2 Post Driver and Compressor. Capable of driving the pilot
probe and the sampling probe into the landfill. The Kitty Hawk portable
post driver has been found to be acceptable.
6.6 Auger Procedure. The following are needed only if the tester
chooses to use the procedure described in Section 8.2.2.
6.6.1 Auger. Capable of drilling through the landfill cover and to
a depth of no less than 0.9 m (3 ft) into the landfill.
6.6.2 Pea Gravel.
6.6.3 Bentonite.
6.7 NMOC Analyzer, Barometer, Thermometer, and Syringes. Same as
in Sections 6.3.1, 6.3.2, 6.33, and 6.2.10, respectively, of Method 25.

7.0 Reagents and Standards

7.1 NMOC Analysis. Same as in Method 25, Section 7.2.
7.2 Calibration. Same as in Method 25, Section 7.4, except omit
Section 7.4.3.
7.3 Quality Assurance Audit Samples.
7.3.1 It is recommended, but not required, that a performance
audit sample be analyzed in conjunction with the field samples. The
audit sample should be in a suitable sample matrix at a concentration
similar to the actual field samples.
7.3.2 When making compliance determinations, and upon
availability, audit samples may be obtained from the appropriate EPA
Regional Office or from the responsible enforcement authority and
analyzed in conjunction with the field samples.

Note: The responsible enforcement authority 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

8.1 Sample Tank Evacuation and Leak-Check. Conduct the sample tank
evacuation and leak-check either in the laboratory or the field.
Connect the pressure gauge and sampling valve to the sample tank.
Evacuate the sample tank to 10 mm Hg (5.4 in H2O) absolute
pressure or less. Close the sampling valve, and allow the tank to sit
for 30 minutes. The tank is acceptable if no change more than
2 mm is noted. Include the results of the leak-check in
the test report.
8.2 Sample Probe Installation. The tester may use the procedure in
Section 8.2.1 or 8.2.2.
8.2.1 Pilot Probe Procedure. Use the post driver to drive the
pilot probe at least 0.9 m (3 ft) below the landfill cover. Alternative
procedures to drive the probe into the landfill may be used subject to
the approval of the Administrator's designated representative.
8.2.1.1 Remove the pilot probe and drive the sample probe into the
hole left by the pilot probe. The sample probe shall extend at least
0.9 m (3 ft) below the landfill cover and shall protrude about 0.3 m (1
ft) above the landfill cover. Seal around the sampling probe with
bentonite and cap the sampling probe with the sampling probe cap.
8.2.2 Auger Procedure. Use an auger to drill a hole to at least
0.9 m (3 ft) below the landfill cover. Place the sample probe in the
hole and backfill with pea gravel to a level 0.6 m (2 ft) from the
surface. The sample probe shall protrude at least 0.3 m (1 ft) above
the landfill cover. Seal the remaining area around the probe with
bentonite. Allow 24 hours for the landfill gases to equilibrate inside
the augured probe before sampling.
8.3 Sample Train Assembly. Just before assembling the sample
train, measure the sample tank vacuum using the pressure gauge. Record
the vacuum, the ambient temperature, and the barometric pressure at
this time. Assemble the sampling probe purging system as shown in
Figure
25C-1.
8.4 Sampling Procedure. Open the sampling valve and use the purge
pump and the flow control valve to evacuate at least two sample probe
volumes from the system at a flow rate of 500 ml/min or less. Close the
sampling valve and replace the purge pump with the sample tank
apparatus as shown in Figure 25C-2. Open the sampling valve and the
sample tank valve and, using the flow control valve, sample at a flow
rate of 500 ml/min or less until either a constant flow rate can no
longer be maintained because of reduced sample tank vacuum or the
appropriate composite volume is attained. Disconnect the sampling tank
apparatus and pressurize the sample cylinder to approximately 1,060 mm
Hg (567 in. H2O) absolute pressure with helium, and record
the final pressure. Alternatively, the sample tank may be pressurized
in the lab.
8.4.1 The following restrictions apply to compositing samples from
different probe sites into a single cylinder: (1) Individual composite
samples per cylinder must be of equal volume; this must be verified by
recording the flow rate, sampling time, vacuum readings, or other
appropriate volume measuring data, (2) individual composite samples
must have a minimum volume of 1 liter unless data is provided showing
smaller volumes can be accurately measured, and (3) composite samples
must not be collected using the final cylinder vacuum as it diminishes
to ambient pressure.
8.4.2 Use Method 3C to determine the percent N2 in each
cylinder. The presence of N2 indicates either infiltration
of ambient air into the landfill gas sample or an inappropriate testing
site has been chosen where anaerobic decomposition has not begun. The
landfill gas sample is acceptable if the concentration of N2
is less than 20 percent. Alternatively, Method 3C may be used to
determine the oxygen content of each cylinder as an air infiltration
test. With this option, the oxygen content of each cylinder must be
less than 5 percent.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

[[Page 62068]]

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.4.1......................... Verify that Ensures that ambient
landfill gas air was not drawn
sample contains into the landfill
less than 20 gas sample.
percent N2 or 5
percent O2.
10.1, 10.2.................... NMOC analyzer Ensures precision of
initial and analytical results.
daily
performance
checks.
11.1.4........................ Audit Sample Evaluate analytical
Analyses. technique and
instrument
calibration.
------------------------------------------------------------------------

10.0 Calibration and Standardization

Note: Maintain a record of performance of each item.

10.1 Initial NMOC Analyzer Performance Test. Same as in Method 25,
Section 10.1, except omit the linearity checks for CO2
standards.
10.2 NMOC Analyzer Daily Calibration.
10.2.1 NMOC Response Factors. Same as in Method 25, Section
10.2.2.
10.3 Sample Tank Volume. The volume of the gas sampling tanks must
be determined. Determine the tank volumes by weighing them empty and
then filled with deionized water; weigh to the nearest 5 g, and record
the results. Alternatively, measure the volume of water used to fill
them to the nearest 5 ml.

11.0 Analytical Procedures

11.1 The oxidation, reduction, and measurement of NMOC's is
similar to Method 25. Before putting the NMOC analyzer into routine
operation, conduct an initial performance test. Start the analyzer, and
perform all the necessary functions in order to put the analyzer into
proper working order. Conduct the performance test according to the
procedures established in Section 10.1. Once the performance test has
been successfully completed and the NMOC calibration response factor
has been determined, proceed with sample analysis as follows:
11.1.1 Daily Operations and Calibration Checks. Before and
immediately after the analysis of each set of samples or on a daily
basis (whichever occurs first), conduct a calibration test according to
the procedures established in Section 10.2. If the criteria of the
daily calibration test cannot be met, repeat the NMOC analyzer
performance test (Section 10.1) before proceeding.
11.1.2 Operating Conditions. Same as in Method 25, Section 11.2.1.
11.1.3 Analysis of Sample Tank. Purge the sample loop with sample,
and then inject the sample. Under the specified operating conditions,
the CO2 in the sample will elute in approximately 100
seconds. As soon as the detector response returns to baseline following
the CO2 peak, switch the carrier gas flow to backflush, and
raise the column oven temperature to 195 deg.C (383 deg.F) as rapidly
as possible. A rate of 30 deg.C/min (54 deg.F/min) has been shown to be
adequate. Record the value obtained for any measured NMOC. Return the
column oven temperature to 85 deg.C (185 deg.F) in preparation for the
next analysis. Analyze each sample in triplicate, and report the
average as Ctm.
11.2 Audit Sample Analysis. When the method is used to analyze
samples to demonstrate compliance with a source emission regulation, an
audit sample, if available, must be analyzed.
11.2.1 Concurrently analyze the audit sample and the compliance
samples in the same manner to evaluate the technique of the analyst and
the standards preparation.
11.2.2 The same analyst, analytical reagents, and analytical
system must be used for the compliance samples and the audit sample. If
this condition is met, duplicate auditing of subsequent compliance
analyses for the same enforcement agency within a 30-day period is
waived. An audit sample set may not be used to validate different sets
of compliance samples under the jurisdiction of separate enforcement
agencies, unless prior arrangements have been made with both
enforcement agencies.
11.3 Audit Sample Results.
11.3.1 Calculate the audit sample concentrations and submit
results using the instructions provided with the audit samples.
11.3.2 Report the results of the audit samples and the compliance
determination samples along with their identification numbers, and the
analyst's name to the responsible enforcement authority. Include this
information with reports of any subsequent compliance analyses for the
same enforcement authority during the 30-day period.
11.3.3 The concentrations of the audit samples obtained by the
analyst must agree within 20 percent of the actual concentration. If
the 20-percent specification is not met, reanalyze the compliance and
audit samples, and include initial and reanalysis values in the test
report.
11.3.4 Failure to meet the 20-percent specification may require
retests until the audit problems are resolved. However, if the audit
results do not affect the compliance or noncompliance status of the
affected facility, the Administrator may waive the reanalysis
requirement, further audits, or retests and accept the results of the
compliance test. While steps are being taken to resolve audit analysis
problems, the Administrator may also choose to use the data to
determine the compliance or noncompliance status of the affected
facility.

12.0 Data Analysis and Calculations

Note: All equations are written using absolute pressure;
absolute pressures are determined by adding the measured barometric
pressure to the measured gauge or manometer pressure.

12.1 Nomenclature.

Bw = Moisture content in the sample, fraction.
CN2 = Measured N2 concentration, fraction.
Ct = Calculated NMOC concentration, ppmv C equivalent.
Ctm = Measured NMOC concentration, ppmv C equivalent.
Pb = Barometric pressure, mm Hg.
Pt = Gas sample tank pressure after sampling, but before
pressurizing, mm Hg absolute.
Ptf = Final gas sample tank pressure after pressurizing, mm
Hg absolute.
Pti = Gas sample tank pressure after evacuation, mm Hg
absolute.
Pw = Vapor pressure of H2O (from Table 25C-1), mm
Hg.
r = Total number of analyzer injections of sample tank during analysis
(where j = injection number, 1 * * * r).
Tt = Sample tank temperature at completion of sampling,
deg.K.
Tti = Sample tank temperature before sampling, deg.K.
Ttf = Sample tank temperature after pressurizing, deg.K.

12.2 Water Correction. Use Table 25C-1 (Section 17.0), the LFG
temperature, and barometric pressure at the sampling site to calculate
Bw.
[GRAPHIC] [TIFF OMITTED] TR17OC00.383

12.3 NMOC Concentration. Use the following equation to calculate
the concentration of NMOC for each sample tank.

[[Page 62069]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.384

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Salo, Albert E., Samuel Witz, and Robert D. MacPhee.
Determination of Solvent Vapor Concentrations by Total Combustion
Analysis: A Comparison of Infrared with Flame Ionization Detectors.
Paper No. 75-33.2. (Presented at the 68th Annual Meeting of the Air
Pollution Control Association. Boston, Massachusetts. June 15-20,
1975.)
14 p.
2. Salo, Albert E., William L. Oaks, and Robert D. MacPhee.
Measuring the Organic Carbon Content of Source Emissions for Air
Pollution Control. Paper No. 74-190. (Presented at the 67th Annual
Meeting of the Air Pollution Control Association. Denver, Colorado.
June 9-13, 1974.) 25 p.
BILLING CODE 6560-50-P

[[Page 62070]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.385

BILLING CODE 6560-50-C

[[Page 62071]]

Table 25C-1.--Moisture Correction
------------------------------------------------------------------------
Vapor Vapor
Pressure Temperature, Pressure
Temperature, deg.C of H2O, deg.C of H2O,
mm Hg mm Hg
------------------------------------------------------------------------
4................................... 6.1 18 15.5
6................................... 7.0 20 17.5
8................................... 8.0 22 19.8
10.................................. 9.2 24 22.4
12.................................. 10.5 26 25.2
14.................................. 12.0 28 28.3
16.................................. 13.6 30 31.8
------------------------------------------------------------------------

Method 25D--Determination of the Volatile Organic Concentration of
Waste Samples

Note: Performance of this method should not be attempted by
persons unfamiliar with the operation of a flame ionization detector
(FID) or an electrolytic conductivity detector (ELCD) because
knowledge beyond the scope of this presentation is required.

1.0 Scope and Application

1.1 Analyte. Volatile Organic Compounds. No CAS No. assigned.
1.2 Applicability. This method is applicable for determining the
volatile organic (VO) concentration of a waste sample.

2.0 Summary of Method

2.1 Principle. A sample of waste is obtained at a point which is
most representative of the unexposed waste (where the waste has had
minimum opportunity to volatilize to the atmosphere). The sample is
suspended in an organic/aqueous matrix, then heated and purged with
nitrogen for 30 min. in order to separate certain organic compounds.
Part of the sample is analyzed for carbon concentration, as methane,
with an FID, and part of the sample is analyzed for chlorine
concentration, as chloride, with an ELCD. The VO concentration is the
sum of the carbon and chlorine content of the sample.

3.0 Definitions

3.1 Well-mixed in the context of this method refers to turbulent
flow which results in multiple-phase waste in effect behaving as
single-phase waste due to good mixing.

4.0 Interferences. [Reserved]

5.0 Safety

6.0 Equipment and Supplies

Note: Mention of trade names or specific products does not
constitute endorsement by the Environmental Protection Agency.

6.1 Sampling. The following equipment is required:
6.1.1 Sampling Tube. Flexible Teflon, 0.25 in. ID (6.35 mm).
6.1.2 Sample Container. Borosilicate glass, 40-mL, and a Teflon-
lined screw cap capable of forming an air tight seal.
6.1.3 Cooling Coil. Fabricated from 0.25 in (6.35 mm). ID 304
stainless steel tubing with a thermocouple at the coil outlet.
6.2 Analysis. The following equipment is required.
6.2.1 Purging Apparatus. For separating the VO from the waste
sample. A schematic of the system is shown in Figure 25D-1. The purging
apparatus consists of the following major components.
6.2.1.1 Purging Flask. A glass container to hold the sample while
it is heated and purged with dry nitrogen. The cap of the purging flask
is equipped with three fittings: one for a purging lance (fitting with
the #7 Ace-thread), one for the Teflon exit tubing (side fitting, also
a #7 Ace-thread), and a third (a 50-mm Ace-thread) to attach the base
of the purging flask as shown in Figure 25D-2. The base of the purging
flask is a 50-mm ID (2 in) cylindrical glass tube. One end of the tube
is open while the other end is sealed. Exact dimensions are shown in
Figure 25D-2.
6.2.1.2 Purging Lance. Glass tube, 6-mm OD (0.2 in) by 30 cm (12
in) long. The purging end of the tube is fitted with a four-arm bubbler
with each tip drawn to an opening 1 mm (0.04 in) in diameter. Details
and exact dimensions are shown in Figure 25D-2.
6.2.1.3 Coalescing Filter. Porous fritted disc incorporated into a
container with the same dimensions as the purging flask. The details of
the design are shown in Figure 25D-3.
6.2.1.4 Constant Temperature Chamber. A forced draft oven capable
of maintaining a uniform temperature around the purging flask and
coalescing filter of 75 2 deg.C (167
3.6 deg.F).
6.2.1.5 Three-way Valve. Manually operated, stainless steel. To
introduce calibration gas into system.
6.2.1.6 Flow Controllers. Two, adjustable. One capable of
maintaining a purge gas flow rate of 6 0.06 L/min (0.2
0.002 ft3/min) The other capable of maintaining
a calibration gas flow rate of 1-100 mL/min (0.00004-0.004
ft3/min).
6.2.1.7 Rotameter. For monitoring the air flow through the purging
system (0-10 L/min)(0-0.4 ft3/min).
6.2.1.8 Sample Splitters. Two heated flow restrictors (placed
inside oven or heated to 120 10 deg.C (248 18
deg.F) ). At a purge rate of 6 L/min (0.2 ft3/min), one
will supply a constant flow to the first detector (the rest of the flow
will be directed to the second sample splitter). The second splitter
will split the analytical flow between the second detector and the flow
restrictor. The approximate flow to the FID will be 40 mL/min (0.0014
ft3/min) and to the ELCD will be 15 mL/min (0.0005
ft3/min), but the exact flow must be adjusted to be
compatible with the individual detector and to meet its linearity
requirement. The two sample splitters will be connected to each other
by 1/8" OD (3.175 mm) stainless steel tubing.
6.2.1.9 Flow Restrictor. Stainless steel tubing, 1/8" OD (3.175
mm), connecting the second sample splitter to the ice bath. Length is
determined by the resulting pressure in the purging flask (as measured
by the pressure gauge). The resulting pressure from the use of the flow
restrictor shall be 6-7 psig.
6.2.1.10 Filter Flask. With one-hole stopper. Used to hold ice
bath. Excess purge gas is vented through the flask to prevent
condensation in the flowmeter and to trap volatile organic compounds.
6.2.1.11 Four-way Valve. Manually operated, stainless steel.
Placed inside oven, used to bypass purging flask.
6.2.1.12 On/Off Valves. Two, stainless steel. One heat resistant
up to 130 deg.C (266 deg.F) and placed between oven and ELCD. The
other a toggle valve used to control purge gas flow.
6.2.1.13 Pressure Gauge. Range 0-40 psi. To monitor pressure in
purging flask and coalescing filter.
6.2.1.14 Sample Lines. Teflon, 1/4" OD (6.35 mm), used inside the
oven to carry purge gas to and from purging chamber and to and from
coalescing filter to four-way valve. Also used to carry sample from
four-way valve to first sample splitter.
6.2.1.15 Detector Tubing. Stainless steel, 1/8" OD (3.175 mm),
heated to 120 10 deg.C (248 18 deg.F) . Used
to carry sample gas from each sample splitter to a detector. Each piece
of tubing must be wrapped with heat tape and insulating tape in order
to insure that no cold spots exist. The tubing leading to the ELCD will
also contain a heat-resistant on-off valve (Section 6.2.1.12) which
shall also be wrapped with heat-tape and insulation.
6.2.2 Volatile Organic Measurement System. Consisting of an FID to
measure

[[Page 62072]]

the carbon concentration of the sample and an ELCD to measure the
chlorine concentration.
6.2.2.1 FID. A heated FID meeting the following specifications is
required.
6.2.2.1.1 Linearity. A linear response ( 5 percent)
over the operating range as demonstrated by the procedures established
in Section 10.1.1.
6.2.2.1.2 Range. A full scale range of 50 pg carbon/sec to 50
g carbon/sec. Signal attenuators shall be available to produce
a minimum signal response of 10 percent of full scale.
6.2.2.1.3 Data Recording System. A digital integration system
compatible with the FID for permanently recording the output of the
detector. The recorder shall have the capability to start and stop
integration at points selected by the operator or it shall be capable
of the ``integration by slices'' technique (this technique involves
breaking down the chromatogram into smaller increments, integrating the
area under the curve for each portion, subtracting the background for
each portion, and then adding all of the areas together for the final
area count).
6.2.2.2 ELCD. An ELCD meeting the following specifications is
required. 1-propanol must be used as the electrolyte. The electrolyte
flow through the conductivity cell shall be 1 to 2 mL/min (0.00004 to
0.00007 ft\3\/min).

Note: A \1/4\-in. ID (6.35 mm) quartz reactor tube is strongly
recommended to reduce carbon buildup and the resulting detector
maintenance.

6.2.2.2.1 Linearity. A linear response ( 10 percent)
over the response range as demonstrated by the procedures in Section
10.1.2.
6.2.2.2.2 Range. A full scale range of 5.0 pg/sec to 500 ng/sec
chloride. Signal attenuators shall be available to produce a minimum
signal response of 10 percent of full scale.
6.2.2.2.3 Data Recording System. A digital integration system
compatible with the output voltage range of the ELCD. The recorder must
have the capability to start and stop integration at points selected by
the operator or it shall be capable of performing the ``integration by
slices'' technique.

7.0 Reagents and Standards

7.1 Sampling.
7.1.1 Polyethylene Glycol (PEG). Ninety-eight percent pure with an
average molecular weight of 400. Before using the PEG, remove any
organic compounds that might be detected as volatile organics by
heating it to 120 deg.C (248 deg.F) and purging it with nitrogen at a
flow rate of 1 to 2 L/min (0.04 to 0.07 ft\3\/min) for 2 hours. The
cleaned PEG must be stored under a 1 to 2 L/min (0.04 to 0.07 ft\3\/
min) nitrogen purge until use. The purge apparatus is shown in Figure
25D-4.
7.2 Analysis.
7.2.1 Sample Separation. The following are required for the sample
purging step.
7.2.1.1 PEG. Same as Section 7.1.1.
7.2.1.2 Purge Gas. Zero grade nitrogen (N2), containing
less than 1 ppm carbon.
7.2.2 Volatile Organics Measurement. The following are required
for measuring the VO concentration.
7.2.2.1 Hydrogen (H2). Zero grade H2, 99.999
percent pure.
7.2.2.2 Combustion Gas. Zero grade air or oxygen as required by
the FID.
7.2.2.3 Calibration Gas. Pressurized gas cylinder containing 10
percent propane and 1 percent 1,1-dichloroethylene by volume in
nitrogen.
7.2.2.4 Water. Deionized distilled water that conforms to American
Society for Testing and Materials Specification D 1193-74, Type 3, is
required for analysis. At the option of the analyst, the
KMnO4 test for oxidizable organic matter may be omitted when
high concentrations are not expected to be present.
7.2.2.5 1-Propanol. ACS grade or better. Electrolyte Solution. For
use in the ELCD.
7.3 Quality Assurance Audit Samples.
7.3.1 It is recommended, but not required, that a performance
audit sample be analyzed in conjunction with the field samples. The
audit sample should be in a suitable sample matrix at a concentration
similar to the actual field samples.
7.3.2 When making compliance determinations, and upon
availability, audit samples may be obtained from the appropriate EPA
regional Office or from the responsible enforcement authority and
analyzed in conjunction with the field samples.

Note: The responsible enforcement authority 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

8.1 Sampling.
8.1.1 Sampling Plan Design and Development. Use the procedures in
chapter nine of Reference 1 in Section 16 as guidance in developing a
sampling plan.
8.1.2 Single Phase or Well-mixed Waste.
8.1.2.1 Install a sampling tap to obtain the sample at a point
which is most representative of the unexposed waste (where the waste
has had minimum opportunity to volatilize to the atmosphere). Assemble
the sampling apparatus as shown in Figure 25D-5.
8.1.2.2 Prepare the sampling containers as follows: Pour 30 mL of
clean PEG into the container. PEG will reduce but not eliminate the
loss of organics during sample collection. Weigh the sample container
with the screw cap, the PEG, and any labels to the nearest 0.01 g and
record the weight (mst). Store the containers in an ice bath
until 1 hour before sampling (PEG will solidify at ice bath
temperatures; allow the containers to reach room temperature before
sampling).
8.1.2.3 Begin sampling by purging the sample lines and cooling
coil with at least four volumes of waste. Collect the purged material
in a separate container and dispose of it properly.
8.1.2.4 After purging, stop the sample flow and direct the
sampling tube to a preweighed sample container, prepared as described
in Section 8.1.2.2. Keep the tip of the tube below the surface of the
PEG during sampling to minimize contact with the atmosphere. Sample at
a flow rate such that the temperature of the waste is less than
10 deg.C (50 deg.F). Fill the sample container and immediately cap it
(within 5 seconds) so that a minimum headspace exists in the container.
Store immediately in a cooler and cover with ice.
8.1.3 Multiple-phase Waste. Collect a 10 g sample of each phase of
waste generated using the procedures described in Section 8.1.2 or
8.1.5. Each phase of the waste shall be analyzed as a separate sample.
Calculate the weighted average VO concentration of the waste using
Equation 25D-13 (Section 12.14).
8.1.4 Solid waste. Add approximately 10 g of the solid waste to a
container prepared in the manner described in Section 8.1.2.2,
minimizing headspace. Cap and chill immediately.
8.1.5 Alternative to Tap Installation. If tap installation is
impractical or impossible, fill a large, clean, empty container by
submerging the container into the waste below the surface of the waste.
Immediately fill a container prepared in the manner described in
Section 8.1.2.2 with approximately 10 g of the waste collected in the
large container. Minimize headspace, cap and chill immediately.
8.1.6 Alternative sampling techniques may be used upon the
approval of the Administrator.
8.2 Sample Recovery.
8.2.1 Assemble the purging apparatus as shown in Figures 25D-1 and
25D-2. The oven shall be heated to

[[Page 62073]]

75 2 deg.C (167 3.6 deg.F). The sampling
lines leading from the oven to the detectors shall be heated to 120
10 deg.C (248 18 deg.F) with no cold spots.
The flame ionization detector shall be operated with a heated block.
Adjust the purging lance so that it reaches the bottom of the chamber.
8.2.2 Remove the sample container from the cooler, and wipe the
exterior of the container to remove any extraneous ice, water, or other
debris. Reweigh the sample container to the nearest 0.01 g, and record
the weight (msf). Pour the contents of the sample container
into the purging flask, rinse the sample container three times with a
total of 20 mL of PEG (since the sample container originally held 30 mL
of PEG, the total volume of PEG added to the purging flask will be 50
mL), transferring the rinsings to the purging flask after each rinse.
Cap purging flask between rinses. The total volume of PEG in the
purging flask shall be 50 mL. Add 50 mL of water to the purging flask.

9.0 Quality Control

9.1 Quality Control Samples. If audit samples are not available,
prepare and analyze the two types of quality control samples (QCS)
listed in Sections 9.4.1 and 9.4.2. Before placing the system in
operation, after a shutdown of greater than six months, and after any
major modifications, analyze each QCS in triplicate. For each detector,
calculate the percent recovery by dividing measured concentration by
theoretical concentration and multiplying by 100. Determine the mean
percent recovery for each detector for each QCS triplicate analysis.
The RSD for any triplicate analysis shall be 10 percent. For
QCS 1 (methylene chloride), the percent recovery shall be 90
percent for carbon as methane, and 55 percent for chlorine
as chloride. For QCS 2 (1,3-dichloro-2-propanol), the percent recovery
shall be 15 percent for carbon as methane, and 6
percent for chlorine as chloride. If the analytical system does not
meet the above-mentioned criteria for both detectors, check the system
parameters (temperature, system pressure, purge rate, etc.), correct
the problem, and repeat the triplicate analysis of each QCS.
9.1.1 QCS 1, Methylene Chloride. Prepare a stock solution by
weighing, to the nearest 0.1 mg, 55 L of HPLC grade methylene
chloride in a tared 5 mL volumetric flask. Record the weight in
milligrams, dilute to 5 mL with cleaned PEG, and inject 100 L
of the stock solution into a sample prepared as a water blank (50 mL of
cleaned PEG and 60 mL of water in the purging flask). Analyze the QCS
according to the procedures described in Sections 10.2 and 10.3,
excluding Section 10.2.2. To calculate the theoretical carbon
concentration (in mg) in QCS 1, multiply mg of methylene chloride in
the stock solution by 3.777 x 10-3. To calculate the
theoretical chlorine concentration (in mg) in QCS 1, multiply mg of
methylene chloride in the stock solution by 1.670 x 10-2.
9.1.2 QCS 2, 1,3-dichloro-2-propanol. Prepare a stock solution by
weighing, to the nearest 0.1 mg, 60 L of high purity grade
1,3-dichloro-2-propanol in a tared 5 mL volumetric flask. Record the
weight in milligrams, dilute to 5 mL with cleaned PEG, and inject 100
L of the stock solution into a sample prepared as a water
blank (50 mL of cleaned PEG and 60 mL of water in the purging flask).
Analyze the QCS according to the procedures described in Sections 10.2
and 10.3, excluding Section 10.2.2. To calculate the theoretical carbon
concentration (in mg) in QCS 2, multiply mg of 1,3-dichloro-2-propanol
in the stock solution by 7.461 x 10-3. To calculate the
theoretical chlorine concentration (in mg) in QCS 2, multiply mg of
1,3-dichloro-2-propanol in the stock solution by 1.099 x
10-2.
9.1.3 Routine QCS Analysis. For each set of compliance samples (in
this context, set is per facility, per compliance test), analyze one
QCS 1 and one QCS 2 sample. The percent recovery for each sample for
each detector shall be 13 percent of the mean recovery
established for the most recent set of QCS triplicate analysis (Section
9.4). If the sample does not meet this criteria, check the system
components and analyze another QCS 1 and 2 until a single set of QCS
meet the 13 percent criteria.

10.0 Calibration and Standardization

10.1 Initial Performance Check of Purging System. Before placing
the system in operation, after a shutdown of greater than six months,
after any major modifications, and at least once per month during
continuous operation, conduct the linearity checks described in
Sections 10.1.1 and 10.1.2. Install calibration gas at the three-way
calibration gas valve. See Figure 25D-1.
10.1.1 Linearity Check Procedure. Using the calibration standard
described in Section 7.2.2.3 and by varying the injection time, it is
possible to calibrate at multiple concentration levels. Use Equation
25D-3 to calculate three sets of calibration gas flow rates and run
times needed to introduce a total mass of carbon, as methane,
(mc) of 1, 5, and 10 mg into the system (low, medium and
high FID calibration, respectively). Use Equation 25D-4 to calculate
three sets of calibration gas flow rates and run times needed to
introduce a total chloride mass (mch) of 1, 5, and 10 mg
into the system (low, medium and high ELCD calibration, respectively).
With the system operating in standby mode, allow the FID and the ELCD
to establish a stable baseline. Set the secondary pressure regulator of
the calibration gas cylinder to the same pressure as the purge gas
cylinder and set the proper flow rate with the calibration flow
controller (see Figure 25D-1). The calibration gas flow rate can be
measured with a flowmeter attached to the vent position of the
calibration gas valve. Set the four-way bypass valve to standby
position so that the calibration gas flows through the coalescing
filter only. Inject the calibration gas by turning the calibration gas
valve from vent position to inject position. Continue the calibration
gas flow for the appropriate period of time before switching the
calibration valve to vent position. Continue recording the response of
the FID and the ELCD for 5 min after switching off calibration gas
flow. Make triplicate injections of all six levels of calibration.
10.1.2 Linearity Criteria. Calculate the average response factor
(Equations 25D-5 and 25D-6) and the relative standard deviation (RSD)
(Equation 25D-10) at each level of the calibration curve for both
detectors. Calculate the overall mean of the three response factor
averages for each detector. The FID linearity is acceptable if each
response factor is within 5 percent of the overall mean and if the RSD
for each set of triplicate injections is less than 5 percent. The ELCD
linearity is acceptable if each response factor is within 10 percent of
the overall mean and if the RSD for each set of triplicate injections
is less than 10 percent. Record the overall mean value of the response
factors for the FID and the ELCD. If the calibration for either the FID
or the ELCD does not meet the criteria, correct the detector/system
problem and repeat Sections 10.1.1 and 10.1.2.
10.2 Daily Calibrations.
10.2.1 Daily Linearity Check. Follow the procedures outlined in
Section 10.1.1 to analyze the medium level calibration for both the FID
and the ELCD in duplicate at the start of the day. Calculate the
response factors and the RSDs for each detector. For the FID, the
calibration is acceptable if the average response factor is within 5
percent of the overall mean response factor (Section 10.1.2) and if the
RSD for the duplicate injection is less than 5 percent. For the ELCD,
the calibration is acceptable if the average response factor

[[Page 62074]]

is within 10 percent of the overall mean response factor (Section
10.1.2) and if the RSD for the duplicate injection is less than 10
percent. If the calibration for either the FID or the ELCD does not
meet the criteria, correct the detector/system problem and repeat
Sections 10.1.1 and 10.1.2.
10.2.2 Calibration Range Check.
10.2.2.1 If the waste concentration for either detector falls
below the range of calibration for that detector, use the procedure
outlined in Section 10.1.1 to choose two calibration points that
bracket the new target concentration. Analyze each of these points in
triplicate (as outlined in Section 10.1.1) and use the criteria in
Section 10.1.2 to determine the linearity of the detector in this
``mini-calibration'' range.
10.2.2.2 After the initial linearity check of the mini-calibration
curve, it is only necessary to test one of the points in duplicate for
the daily calibration check (in addition to the points specified in
Section 10.2.1). The average daily mini-calibration point should fit
the linearity criteria specified in Section 10.2.1. If the calibration
for either the FID or the ELCD does not meet the criteria, correct the
detector/system problem and repeat the calibration procedure mentioned
in the first paragraph of Section 10.2.2. A mini-calibration curve for
waste concentrations above the calibration curve for either detector is
optional.
10.3 Analytical Balance. Calibrate against standard weights.

11.0 Analysis

11.1 Sample Analysis.
11.1.1 Turn on the constant temperature chamber and allow the
temperature to equilibrate at 75 2 deg.C (167
3.6 deg.F). Turn the four-way valve so that the purge gas bypasses the
purging flask, the purge gas flowing through the coalescing filter and
to the detectors (standby mode). Turn on the purge gas. Allow both the
FID and the ELCD to warm up until a stable baseline is achieved on each
detector. Pack the filter flask with ice. Replace ice after each run
and dispose of the waste water properly. When the temperature of the
oven reaches 75 2 deg.C (167 3.6 deg.F),
start both integrators and record baseline. After 1 min, turn the four-
way valve so that the purge gas flows through the purging flask, to the
coalescing filter and to the sample splitters (purge mode). Continue
recording the response of the FID and the ELCD. Monitor the readings of
the pressure gauge and the rotameter. If the readings fall below
established setpoints, stop the purging, determine the source of the
leak, and resolve the problem before resuming. Leaks detected during a
sampling period invalidate that sample.
11.1.2 As the purging continues, monitor the output of the
detectors to make certain that the analysis is proceeding correctly and
that the results are being properly recorded. Every 10 minutes read and
record the purge flow rate, the pressure and the chamber temperature.
Continue the purging for 30 minutes.
11.1.3 For each detector output, integrate over the entire area of
the peak starting at 1 minute and continuing until the end of the run.
Subtract the established baseline area from the peak area. Record the
corrected area of the peak. See Figure 25D-6 for an example
integration.
11.2 Water Blank. A water blank shall be analyzed for each batch
of cleaned PEG prepared. Transfer about 60 mL of water into the purging
flask. Add 50 mL of the cleaned PEG to the purging flask. Treat the
blank as described in Sections 8.2 and 8.3, excluding Section 8.2.2.
Calculate the concentration of carbon and chlorine in the blank sample
(assume 10 g of waste as the mass). A VO concentration equivalent to
10 percent of the applicable standard may be subtracted from
the measured VO concentration of the waste samples. Include all blank
results and documentation in the test report.
11.3 Audit Sample Analysis.
11.3.1 When the method is used to analyze samples to demonstrate
compliance with a source emission regulation, an audit sample, if
available, must be analyzed.
11.3.2 Concurrently analyze the audit sample and the compliance
samples in the same manner to evaluate the technique of the analyst and
the standards preparation.
11.3.3 The same analyst, analytical reagents, and analytical
system must be used for the compliance samples and the audit sample. If
this condition is met, duplicate auditing of subsequent compliance
analyses for the same enforcement agency within a 30-day period is
waived. An audit sample may not be used to validate different sets of
compliance samples under the jurisdiction of separate enforcement
agencies, unless prior arrangements have been made with both
enforcement agencies.
11.4 Audit Sample Results.
11.4.1 Calculate the audit sample concentrations and submit
results using the instructions provided with the audit samples.
11.4.2 Report the results of the audit samples and the compliance
determination samples along with their identification numbers, and the
analyst's name to the responsible enforcement authority. Include this
information with reports of any subsequent compliance analyses for the
same enforcement authority during the 30-day period.

12.0 Data Analysis and Calculations

12.1 Nomenclature.

Ab = Area under the water blank response curve, counts.
Ac = Area under the calibration response curve, counts.
As = Area under the sample response curve, counts.
C = Concentration of volatile organics in the sample, ppmw.
Cc = Concentration of carbon, as methane, in the calibration
gas, mg/L.
Cch = Concentration of chloride in the calibration gas, mg/
L.
Cj = VO concentration of phase j, ppmw.
DRt = Average daily response factor of the FID, mg
CH4/counts.
Drth = Average daily response factor of the ELCD, mg
Cl-/counts.
Fj = Weight fraction of phase j present in the waste.
mc = Mass of carbon, as methane, in a calibration run, mg.
mch = Mass of chloride in a calibration run, mg.
ms = Mass of the waste sample, g.
msc = Mass of carbon, as methane, in the sample, mg.
msf = Mass of sample container and waste sample, g.
msh = Mass of chloride in the sample, mg.
mst = Mass of sample container prior to sampling, g.
mVO = Mass of volatile organics in the sample, mg.
n = Total number of phases present in the waste.
Pp = Percent propane in calibration gas (L/L).
Pvc = Percent 1,1-dichloroethylene in calibration gas (L/L).
Qc = Flow rate of calibration gas, L/min.
tc = Length of time standard gas is delivered to the
analyzer, min.
W = Weighted average VO concentration, ppmw.

12.2 Concentration of Carbon, as Methane, in the Calibration Gas.

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[GRAPHIC] [TIFF OMITTED] TR17OC00.386

12.3 Concentration of Chloride in the Calibration Gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.387

12.4 Mass of Carbon, as Methane, in a Calibration Run.
[GRAPHIC] [TIFF OMITTED] TR17OC00.388

12.5 Mass of Chloride in a Calibration Run.
[GRAPHIC] [TIFF OMITTED] TR17OC00.389

12.6 FID Response Factor, mg/counts.
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12.7 ELCD Response Factor, mg/counts.
[GRAPHIC] [TIFF OMITTED] TR17OC00.391

12.8 Mass of Carbon in the Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.392

12.9 Mass of Chloride in the Sample.
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12.10 Mass of Volatile Organics in the Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.394

12.11 Relative Standard Deviation.
[GRAPHIC] [TIFF OMITTED] TR17OC00.395

12.12 Mass of Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.396

12.13 Concentration of Volatile Organics in Waste.
[GRAPHIC] [TIFF OMITTED] TR17OC00.397

12.14 Weighted Average VO Concentration of Multi-phase Waste.
[GRAPHIC] [TIFF OMITTED] TR17OC00.398

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. ``Test Methods for Evaluating Solid Waste, Physical/Chemistry
Methods'', U.S. Environmental Protection Agency. Publication SW-846,
3rd Edition, November 1986 as amended by Update I, November 1990.
BILLING CODE 6560-50-P

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17.0 Tables, Diagrams, Flowcharts, and Validation Data
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[[Page 62082]]

Method 25E--Determination of Vapor Phase Organic Concentration in
Waste Samples

Note:
Performance of this method should not be attempted by persons
unfamiliar with the operation of a flame ionization detector (FID)
nor by those who are unfamiliar with source sampling because
knowledge beyond the scope of this presentation is required. This
method is not inclusive with respect to specifications (e.g.,
reagents and standards) and calibration procedures. Some material is
incorporated by reference from other methods. Therefore, to obtain
reliable results, persons using this method should have a thorough
knowledge of at least the following additional test methods: Method
106, part 61, Appendix B, and Method 18, part 60, Appendix A.

1.0 Scope and Application

1.1 Applicability. This method is applicable for determining the
vapor pressure of waste cited by an applicable regulation.
1.2 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 The headspace vapor of the sample is analyzed for carbon
content by a headspace analyzer, which uses an FID.

3.0 Definitions. [Reserved]

4.0 Interferences

4.1 The analyst shall select the operating parameters best suited
to the requirements for a particular analysis. The analyst shall
produce confirming data through an adequate supplemental analytical
technique and have the data available for review by the Administrator.

5.0 Safety. [Reserved]

6.0 Equipment and Supplies

6.1 Sampling. The following equipment is required:
6.1.1 Sample Containers. Vials, glass, with butyl rubber septa,
Perkin-Elmer Corporation Numbers 0105-0129 (glass vials), B001-0728
(gray butyl rubber septum, plug style), 0105-0131 (butyl rubber septa),
or equivalent. The seal must be made from butyl rubber. Silicone rubber
seals are not acceptable.
6.1.2 Vial Sealer. Perkin-Elmer Number 105-0106, or equivalent.
6.1.3 Gas-Tight Syringe. Perkin-Elmer Number 00230117, or
equivalent.
6.1.4 The following equipment is required for sampling.
6.1.4.1 Tap.
6.1.4.2 Tubing. Teflon, 0.25-in. ID.

Note: Mention of trade names or specific products does not
constitute endorsement by the Environmental Protection Agency.

6.1.4.3 Cooling Coil. Stainless steel (304), 0.25 in.-ID, equipped
with a thermocouple at the coil outlet.
6.2 Analysis. The following equipment is required.
6.2.1 Balanced Pressure Headspace Sampler. Perkin-Elmer HS-6, HS-
100, or equivalent, equipped with a glass bead column instead of a
chromatographic column.
6.2.2 FID. An FID meeting the following specifications is
required.
6.2.2.1 Linearity. A linear response (5 percent) over
the operating range as demonstrated by the procedures established in
Section 10.2.
6.2.2.2 Range. A full scale range of 1 to 10,000 parts per million
(ppm) propane (C3H8). Signal attenuators shall be
available to produce a minimum signal response of 10 percent of full
scale.
6.2.3 Data Recording System. Analog strip chart recorder or
digital integration system compatible with the FID for permanently
recording the output of the detector.
6.2.4 Temperature Sensor. Capable of reading temperatures in the
range of 30 to 60 deg.C (86 to 140 deg.F) with an accuracy of
0.1 deg.C (0.2 deg.F).

7.0 Reagents and Standards

7.1 Analysis. The following items are required for analysis.
7.1.1 Hydrogen (H2). Zero grade hydrogen, as required
by the FID.
7.1.2 Carrier Gas. Zero grade nitrogen, containing less than 1 ppm
carbon (C) and less than 1 ppm carbon dioxide.
7.1.3 Combustion Gas. Zero grade air or oxygen as required by the
FID.
7.2 Calibration and Linearity Check.
7.2.1 Stock Cylinder Gas Standard. 100 percent propane. The
manufacturer shall: (a) Certify the gas composition to be accurate to
3 percent or better (see Section 7.2.1.1); (b) recommend a
maximum shelf life over which the gas concentration does not change by
greater than 5 percent from the certified value; and (c)
affix the date of gas cylinder preparation, certified propane
concentration, and recommended maximum shelf life to the cylinder
before shipment to the buyer.
7.2.1.1 Cylinder Standards Certification. The manufacturer shall
certify the concentration of the calibration gas in the cylinder by (a)
directly analyzing the cylinder and (b) calibrating his analytical
procedure on the day of cylinder analysis. To calibrate his analytical
procedure, the manufacturer shall use, as a minimum, a three-point
calibration curve.
7.2.1.2 Verification of Manufacturer's Calibration Standards.
Before using, the manufacturer shall verify each calibration standard
by (a) comparing it to gas mixtures prepared in accordance with the
procedure described in Section 7.1 of Method 106 of Part 61, Appendix
B, or by (b) calibrating it against Standard Reference Materials
(SRM's) prepared by the National Bureau of Standards, if such SRM's are
available. The agreement between the initially determined concentration
value and the verification concentration value must be within
5 percent. The manufacturer must reverify all calibration
standards on a time interval consistent with the shelf life of the
cylinder standards sold.

8.0 Sampling Collection, Preservation, Storage, and Transport

8.1 Install a sampling tap to obtain a sample at a point which is
most representative of the unexposed waste (where the waste has had
minimum opportunity to volatilize to the atmosphere). Assemble the
sampling apparatus as shown in Figure 25E-1.
8.2 Begin sampling by purging the sample lines and cooling coil
with at least four volumes of waste. Collect the purged material in a
separate container and dispose of it properly.
8.3 After purging, stop the sample flow and transfer the Teflon
sampling tube to a sample container. Sample at a flow rate such that
the temperature of the waste is 10 deg.C (50 deg.F). Fill the sample
container halfway (5 percent) and cap it within 5 seconds.
Store immediately in a cooler and cover with ice.
8.4 Alternative sampling techniques may be used upon the approval
of the Administrator.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.2, 10.3.................... FID calibration Ensure precision of
and response analytical results.
check.
------------------------------------------------------------------------

[[Page 62083]]

10.0 Calibration and Standardization

Note: Maintain a record of performance of each item.

10.1 Use the procedures in Sections 10.2 to calibrate the
headspace analyzer and FID and check for linearity before the system is
first placed in operation, after any shutdown longer than 6 months, and
after any modification of the system.
10.2 Calibration and Linearity. Use the procedures in Section 10
of Method 18 of Part 60, Appendix A, to prepare the standards and
calibrate the flowmeters, using propane as the standard gas. Fill the
calibration standard vials halfway (5 percent) with
deionized water. Purge and fill the airspace with calibration standard.
Prepare a minimum of three concentrations of calibration standards in
triplicate at concentrations that will bracket the applicable cutoff.
For a cutoff of 5.2 kPa (0.75 psi), prepare nominal concentrations of
30,000, 50,000, and 70,000 ppm as propane. For a cutoff of 27.6 kPa
(4.0 psi), prepare nominal concentrations of 200,000, 300,000, and
400,000 ppm as propane.
10.2.1 Use the procedures in Section 11.3 to measure the FID
response of each standard. Use a linear regression analysis to
calculate the values for the slope (k) and the y-intercept (b). Use the
procedures in Sections 12.3 and 12.2 to test the calibration and the
linearity.
10.3 Daily FID Calibration Check. Check the calibration at the
beginning and at the end of the daily runs by using the following
procedures. Prepare 2 calibration standards at the nominal cutoff
concentration using the procedures in Section 10.2. Place one at the
beginning and one at the end of the daily run. Measure the FID response
of the daily calibration standard and use the values for k and b from
the most recent calibration to calculate the concentration of the daily
standard. Use an equation similar to 25E-2 to calculate the percent
difference between the daily standard and Cs. If the
difference is within 5 percent, then the previous values for k and b
can be used. Otherwise, use the procedures in Section 10.2 to
recalibrate the FID.

11.0 Analytical Procedures

11.1 Allow one hour for the headspace vials to equilibrate at the
temperature specified in the regulation. Allow the FID to warm up until
a stable baseline is achieved on the detector.
11.2 Check the calibration of the FID daily using the procedures
in Section 10.3.
11.3 Follow the manufacturer's recommended procedures for the
normal operation of the headspace sampler and FID.
11.4 Use the procedures in Sections 12.4 and 12.5 to calculate the
vapor phase organic vapor pressure in the samples.
11.5 Monitor the output of the detector to make certain that the
results are being properly recorded.

12.0 Data Analysis and Calculations

12.1 Nomenclature.

A = Measurement of the area under the response curve, counts.
b = y-intercept of the linear regression line.
Ca = Measured vapor phase organic concentration of sample,
ppm as propane.
Cma = Average measured vapor phase organic concentration of
standard, ppm as propane.
Cm = Measured vapor phase organic concentration of standard,
ppm as propane.
Cs = Calculated standard concentration, ppm as propane.
k = Slope of the linear regression line.
Pbar = Atmospheric pressure at analysis conditions, mm Hg
(in. Hg).
P* = Organic vapor pressure in the sample, kPa (psi).
PD = Percent difference between the average measured vapor phase
organic concentration (Cm) and the calculated standard
concentration (Cs).
RSD = Relative standard deviation.
=1.333 x 10-\7\ kPa/[(mm Hg)(ppm)], (4.91 x
10-\7\ psi/[(in. Hg)(ppm)])

12.2 Linearity. Use the following equation to calculate the
measured standard concentration for each standard vial.
[GRAPHIC] [TIFF OMITTED] TR17OC00.405

12.2.1 Calculate the average measured standard concentration
(Cma) for each set of triplicate standards and use the
following equation to calculate PD between Cma and
Cs. The instrument linearity is acceptable if the PD is
within five for each standard.
[GRAPHIC] [TIFF OMITTED] TR17OC00.406

12.3. Relative Standard Deviation (RSD). Use the following
equation to calculate the RSD for each triplicate set of standards.
[GRAPHIC] [TIFF OMITTED] TR17OC00.407

The calibration is acceptable if the RSD is within five for each
standard concentration.
12.4 Concentration of organics in the headspace. Use the following
equation to calculate the concentration of vapor phase organics in each
sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.408

12.5 Vapor Pressure of Organics in the Headspace Sample. Use the
following equation to calculate the vapor pressure of organics in the
sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.409

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. Salo, Albert E., Samuel Witz, and Robert D. MacPhee.
``Determination of Solvent Vapor Concentrations by Total Combustion
Analysis: a Comparison of Infared with Flame Ionization Detectors.
Paper No. 75-33.2. (Presented at the 68th Annual Meeting of the Air
Pollution Control Association. Boston, Massachusetts.
2. Salo, Albert E., William L. Oaks, and Robert D. MacPhee.
``Measuring the Organic Carbon Content of Source Emissions for Air
Pollution Control. Paper No. 74-190. (Presented at the 67th Annual
Meeting of the Air Pollution Control Association. Denver, Colorado.
June 9-13, 1974.) p. 25.
BILLING CODE 6560-50-P

[[Page 62084]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.412

BILLING CODE 6560-50-C

[[Page 62085]]

Method 26--Determination of Hydrogen Halide and Halogen Emissions
From Stationary Sources Non-Isokinetic Method

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analytes CAS No.
------------------------------------------------------------------------
Hydrogen Chloride (HCl)................................. 7647-01-0
Hydrogen Bromide (HBr).................................. 10035-10-6
Hydrogen Fluoride (HF).................................. 7664-39-3
Chlorine (Cl2).......................................... 7882-50-5
Bromine (Br2)........................................... 7726-95-6
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for determining
emissions of hydrogen halides (HX) (HCl, HBr, and HF) and halogens
(X2) (Cl2 and Br2) from stationary
sources when specified by the applicable subpart. Sources, such as
those controlled by wet scrubbers, that emit acid particulate matter
must be sampled using Method 26A.
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 sample is extracted from the source and passed
through a prepurged heated probe and filter into dilute sulfuric acid
and dilute sodium hydroxide solutions which collect the gaseous
hydrogen halides and halogens, respectively. The filter collects
particulate matter including halide salts but is not routinely
recovered and analyzed. The hydrogen halides are solubilized in the
acidic solution and form chloride (Cl-), bromide
(Br-), and fluoride (F-) ions. The halogens have
a very low solubility in the acidic solution and pass through to the
alkaline solution where they are hydrolyzed to form a proton
(H+), the halide ion, and the hypohalous acid (HClO or
HBrO). Sodium thiosulfate is added in excess to the alkaline solution
to assure reaction with the hypohalous acid to form a second halide ion
such that 2 halide ions are formed for each molecule of halogen gas.
The halide ions in the separate solutions are measured by ion
chromatography (IC).

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Volatile materials, such as chlorine dioxide (ClO2)
and ammonium chloride (NH4Cl), which produce halide ions
upon dissolution during sampling are potential interferents.
Interferents for the halide measurements are the halogen gases which
disproportionate to a hydrogen halide and a hydrohalous acid upon
dissolution in water. However, the use of acidic rather than neutral or
basic solutions for collection of the hydrogen halides greatly reduces
the dissolution of any halogens passing through this solution.
4.2 The simultaneous presence of HBr and CL2 may cause
a positive bias in the HCL result with a corresponding negative bias in
the Cl2 result as well as affecting the HBr/Br2
split.
4.3 High concentrations of nitrogen oxides (NOX) may
produce sufficient nitrate (NO3- to interfere
with measurements of very low Br- levels.
4.4 A glass wool plug should not be used to remove particulate
matter since a negative bias in the data could result.
4.5 There is anecdotal evidence that HF may be outgassed from new
teflon components. If HF is a target analyte, then preconditioning of
new teflon components, by heating should be considered.

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 to establish appropriate safety and health practices and
determine the applicability of regulatory limitations before 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 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.
5.2.2 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. 1 mg/m3 for 8 hours will cause lung damage or, in
higher concentrations, death. Provide ventilation to limit inhalation.
Reacts violently with metals and organics.

6.0 Equipment and Supplies

Note: Mention of trade names or specific products does not
constitute endorsement by the Environmental Protection Agency.

6.1 Sampling. The sampling train is shown in Figure 26-1, and
component parts are discussed below.
6.1.1 Probe. Borosilicate glass, approximately \3/8\-in. (9-mm)
I.D. with a heating system to prevent moisture condensation. A Teflon-
glass filter in a mat configuration should be installed to remove
particulate matter from the gas stream (see Section 6.1.6).
6.1.2 Three-way Stopcock. A borosilicate-glass three-way stopcock
with a heating system to prevent moisture condensation. The heated
stopcock should connect to the outlet of the heated filter and the
inlet of the first impinger. The heating system should be capable of
preventing condensation up to the inlet of the first impinger. Silicone
grease may be used, if necessary, to prevent leakage.
6.1.3 Impingers. Four 30-ml midget impingers with leak-free glass
connectors. Silicone grease may be used, if necessary, to prevent
leakage. For sampling at high moisture sources or for sampling times
greater than one hour, a midget impinger with a shortened stem (such
that the gas sample does not bubble through the collected condensate)
should be used in front of the first impinger.
6.1.4 Drying Tube or Impinger. Tube or impinger, of Mae West
design, filled with 6- to 16-mesh indicating type silica gel, or
equivalent, to dry the gas sample and to protect the dry gas meter and
pump. If the silica gel has been used previously, dry at 175 deg.C
(350 deg.F) for 2 hours. New silica gel may be used as received.
Alternatively, other types of desiccants (equivalent or better) may be
used.
6.1.5 Heating System. Any heating system capable of maintaining a
temperature around the probe and filter holder greater than 120 deg.C
(248 deg.F) during sampling, or such other temperature as specified by
an applicable subpart of the standards or approved by the Administrator
for a particular application.
6.1.6 Filter Holder and Support. The filter holder shall be made
of Teflon or quartz. The filter support shall be made of Teflon. All
Teflon filter holders and supports are available from Savillex Corp.,
5325 Hwy 101, Minnetonka, MN 55345.
6.1.7 Sample Line. Leak-free, with compatible fittings to connect
the last impinger to the needle valve.
6.1.8 Rate Meter. Rotameter, or equivalent, capable of measuring
flow rate to within 2 percent of the selected flow rate of 2 liters/min
(0.07 ft3/min).
6.1.9 Purge Pump, Purge Line, Drying Tube, Needle Valve, and Rate
Meter. Pump capable of purging the

[[Page 62086]]

sampling probe at 2 liters/min, with drying tube, filled with silica
gel or equivalent, to protect pump, and a rate meter capable of
measuring 0 to 5 liters/min (0.2 ft3/min).
6.1.10 Stopcock Grease, Valve, Pump, Volume Meter, Barometer, and
Vacuum Gauge. Same as in Method 6, Sections 6.1.1.4, 6.1.1.7, 6.1.1.8,
6.1.1.10, 6.1.2, and 6.1.3.
6.1.11 Temperature Measuring Devices. Temperature sensors to
monitor the temperature of the probe and to monitor the temperature of
the sampling system from the outlet of the probe to the inlet of the
first impinger.
6.1.12 Ice Water Bath. To minimize loss of absorbing solution.
6.2 Sample Recovery.
6.2.1 Wash Bottles. Polyethylene or glass, 500-ml or larger, two.
6.2.2 Storage Bottles. 100- or 250-ml, high-density polyethylene
bottles with Teflon screw cap liners to store impinger samples.
6.3 Sample Preparation and Analysis. The materials required for
volumetric dilution and chromatographic analysis of samples are
described below.
6.3.1 Volumetric Flasks. Class A, 100-ml size.
6.3.2 Volumetric Pipets. Class A, assortment. To dilute samples to
the calibration range of the ion chromatograph.
6.3.3 Ion Chromatograph (IC). Suppressed or non-suppressed, with a
conductivity detector and electronic integrator operating in the peak
area mode. Other detectors, strip chart recorders, and peak height
measurements may be used.

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 (ACS reagent grade). When
such specifications are not available, the best available grade
shall be used.

7.1 Sampling.
7.1.1 Filter. A 25-mm (1 in) (or other size) Teflon glass mat,
Pallflex TX40HI75 (Pallflex Inc., 125 Kennedy Drive, Putnam, CT 06260).
This filter is in a mat configuration to prevent fine particulate
matter from entering the sampling train. Its composition is 75% Teflon/
25% borosilicate glass. Other filters may be used, but they must be in
a mat (as opposed to a laminate) configuration and contain at least 75%
Teflon. For practical rather than scientific reasons, when the stack
gas temperature exceeds 210 deg.C (410 deg.F) and the HCl
concentration is greater than 20 ppm, a quartz-fiber filter may be used
since Teflon becomes unstable above this temperature.
7.1.2 Water. Deionized, distilled water that conforms to American
Society of Testing and Materials (ASTM) Specification D 1193-77 or 91,
Type 3 (incorporated by reference--see Sec. 60.17).
7.1.3 Acidic Absorbing Solution, 0.1 N Sulfuric Acid
(H2SO4). To prepare 100 ml of the absorbing
solution for the front impinger pair, slowly add 0.28 ml of
concentrated H2SO4 to about 90 ml of water while
stirring, and adjust the final volume to 100 ml using additional water.
Shake well to mix the solution.
7.1.4 Silica Gel. Indicating type, 6 to 16 mesh. If previously
used, dry at 180 deg.C (350 deg.F) for 2 hours. New silica gel may be
used as received. Alternatively, other types of desiccants may be used,
subject to the approval of the Administrator.
7.1.5 Alkaline Adsorbing Solution, 0.1 N Sodium Hydroxide (NaOH).
To prepare 100 ml of the scrubber solution for the third and fourth
impinger, dissolve 0.40 g of solid NaOH in about 90 ml of water, and
adjust the final solution volume to 100 ml using additional water.
Shake well to mix the solution.
7.1.6 Sodium Thiosulfate (Na2S2O3
5 H2O)
7.2 Sample Preparation and Analysis.
7.2.1 Water. Same as in Section 7.1.2.
7.2.2 Absorbing Solution Blanks. A separate blank solution of each
absorbing reagent should be prepared for analysis with the field
samples. Dilute 30 ml of each absorbing solution to approximately the
same final volume as the field samples using the blank sample of rinse
water.
7.2.3 Halide Salt Stock Standard Solutions. Prepare concentrated
stock solutions from reagent grade sodium chloride (NaCl), sodium
bromide (NaBr), and sodium fluoride (NaF). Each must be dried at
110 deg.C (230 deg.F) for two or more hours and then cooled to room
temperature in a desiccator immediately before weighing. Accurately
weigh 1.6 to 1.7 g of the dried NaCl to within 0.1 mg, dissolve in
water, and dilute to 1 liter. Calculate the exact Cl-
concentration using Equation 26-1 in Section 12.2. In a similar manner,
accurately weigh and solubilize 1.2 to 1.3 g of dried NaBr and 2.2 to
2.3 g of NaF to make 1-liter solutions. Use Equations 26-2 and 26-3 in
Section 12.2, to calculate the Br- and F-
concentrations. Alternately, solutions containing a nominal certified
concentration of 1000 mg/l NaCl are commercially available as
convenient stock solutions from which standards can be made by
appropriate volumetric dilution. Refrigerate the stock standard
solutions and store no longer than one month.
7.2.4 Chromatographic Eluent. Effective eluents for nonsuppressed
IC using a resin-or silica-based weak ion exchange column are a 4 mM
potassium hydrogen phthalate solution, adjusted to pH 4.0 using a
saturated sodium borate solution, and a 4 mM 4-hydroxy benzoate
solution, adjusted to pH 8.6 using 1 N NaOH. An effective eluent for
suppressed ion chromatography is a solution containing 3 mM sodium
bicarbonate and 2.4 mM sodium carbonate. Other dilute solutions
buffered to a similar pH and containing no interfering ions may be
used. When using suppressed ion chromatography, if the ``water dip''
resulting from sample injection interferes with the chloride peak, use
a 2 mM NaOH/2.4 mM sodium bicarbonate eluent.
7.3 Quality Assurance Audit Samples. When making compliance
determinations, and upon availability, audit samples may be obtained
from the appropriate EPA regional Office or from the responsible
enforcement authority.

Note: The responsible enforcement authority 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

Note: Because of the complexity of this method, testers and
analyst should be trained and experienced with the procedure to
ensure reliable results.

8.1 Sampling.
8.1.1 Preparation of Collection Train. Prepare the sampling train
as follows: Pour 15 ml of the acidic absorbing solution into each one
of the first pair of impingers, and 15 ml of the alkaline absorbing
solution into each one of the second pair of impingers. Connect the
impingers in series with the knockout impinger first, if used, followed
by the two impingers containing the acidic absorbing solution and the
two impingers containing the alkaline absorbing solution. Place a fresh
charge of silica gel, or equivalent, in the drying tube or impinger at
the end of the impinger train.
8.1.2 Adjust the probe temperature and the temperature of the
filter and the stopcock, i.e., the heated area in Figure 26-1 to a
temperature sufficient to prevent water condensation. This temperature
should be at least 20 deg.C (68 deg.F) above the source temperature,
and greater than 120 deg.C (248 deg.F). The temperature should be
monitored

[[Page 62087]]

throughout a sampling run to ensure that the desired temperature is
maintained. It is important to maintain a temperature around the probe
and filter of greater than 120 deg.C (248 deg.F) since it is
extremely difficult to purge acid gases off these components. (These
components are not quantitatively recovered and hence any collection of
acid gases on these components would result in potential undereporting
of these emission. The applicable subparts may specify alternative
higher temperatures.)
8.1.3 Leak-Check Procedure.
8.1.3.1 Sampling Train. A leak-check prior to the sampling run is
optional; however, a leak-check after the sampling run is mandatory.
The leak-check procedure is as follows: Temporarily attach a suitable
[e.g., 0-40 cc/min (0-2.4 in\3\/min)] rotameter to the outlet of the
dry gas meter and place a vacuum gauge at or near the probe inlet. Plug
the probe inlet, pull a vacuum of at least 250 mm Hg (10 in. Hg), and
note the flow rate as indicated by the rotameter. A leakage rate not in
excess of 2 percent of the average sampling rate is acceptable.

Note: Carefully release the probe inlet plug before turning off
the pump.

8.1.3.2 Pump. It is suggested (not mandatory) that the pump be
leak-checked separately, either prior to or after the sampling run. If
done prior to the sampling run, the pump leak-check shall precede the
leak-check of the sampling train described immediately above; if done
after the sampling run, the pump leak-check shall follow the train
leak-check. To leak-check the pump, proceed as follows: Disconnect the
drying tube from the probe-impinger assembly. Place a vacuum gauge at
the inlet to either the drying tube or pump, pull a vacuum of 250 mm
(10 in) Hg, plug or pinch off the outlet of the flow meter, and then
turn off the pump. The vacuum should remain stable for at least 30 sec.
Other leak-check procedures may be used, subject to the approval of the
Administrator, U.S. Environmental Protection Agency.
8.1.4 Purge Procedure. Immediately before sampling, connect the
purge line to the stopcock, and turn the stopcock to permit the purge
pump to purge the probe (see Figure 1A of Figure 26-1). Turn on the
purge pump, and adjust the purge rate to 2 liters/min (0.07 ft\3\/min).
Purge for at least 5 minutes before sampling.
8.1.5 Sample Collection. Turn on the sampling pump, pull a slight
vacuum of approximately 25 mm Hg (1 in Hg) on the impinger train, and
turn the stopcock to permit stack gas to be pulled through the impinger
train (see Figure 1C of Figure 26-1). Adjust the sampling rate to 2
liters/min, as indicated by the rate meter, and maintain this rate to
within 10 percent during the entire sampling run. Take readings of the
dry gas meter volume and temperature, rate meter, and vacuum gauge at
least once every five minutes during the run. A sampling time of one
hour is recommended. Shorter sampling times may introduce a significant
negative bias in the HCl concentration. At the conclusion of the
sampling run, remove the train from the stack, cool, and perform a
leak-check as described in Section 8.1.3.1.
8.2 Sample Recovery.
8.2.1 Disconnect the impingers after sampling. Quantitatively
transfer the contents of the acid impingers and the knockout impinger,
if used, to a leak-free storage bottle. Add the water rinses of each of
these impingers and connecting glassware to the storage bottle.
8.2.2 Repeat this procedure for the alkaline impingers and
connecting glassware using a separate storage bottle. Add 25 mg of
sodium thiosulfate per the product of ppm of halogen anticipated to be
in the stack gas times the volume (dscm) of stack gas sampled (0.7 mg
per ppm-dscf).

Note: This amount of sodium thiosulfate includes a safety factor
of approximately 5 to assure complete reaction with the hypohalous
acid to form a second Cl- ion in the alkaline solution.

8.2.3 Save portions of the absorbing reagents (0.1 N
H2SO4 and 0.1 N NaOH) equivalent to the amount
used in the sampling train (these are the absorbing solution blanks
described in Section 7.2.2); dilute to the approximate volume of the
corresponding samples using rinse water directly from the wash bottle
being used. Add the same amount of sodium thiosulfate solution to the
0.1 N NaOH absorbing solution blank. Also, save a portion of the rinse
water used to rinse the sampling train. Place each in a separate,
prelabeled storage bottle. The sample storage bottles should be sealed,
shaken to mix, and labeled. Mark the fluid level.
8.3 Sample Preparation for Analysis. Note the liquid levels in the
storage bottles and confirm on the analysis sheet whether or not
leakage occurred during transport. If a noticeable leakage has
occurred, either void the sample or use methods, subject to the
approval of the Administrator, to correct the final results.
Quantitatively transfer the sample solutions to 100-ml volumetric
flasks, and dilute to 100 ml with water.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
11.2.......................... Audit sample Evaluate analytical
analysis. technique,
preparation of
standards.
------------------------------------------------------------------------

10.0 Calibration and Standardization

Note: Maintain a laboratory log of all calibrations.

10.1 Volume Metering System, Temperature Sensors, Rate Meter, and
Barometer. Same as in Method 6, Sections 10.1, 10.2, 10.3, and 10.4.
10.2 Ion Chromatograph.
10.2.1 To prepare the calibration standards, dilute given amounts
(1.0 ml or greater) of the stock standard solutions to convenient
volumes, using 0.1 N H2SO4 or 0.1 N NaOH, as
appropriate. Prepare at least four calibration standards for each
absorbing reagent containing the appropriate stock solutions such that
they are within the linear range of the field samples.
10.2.2 Using one of the standards in each series, ensure adequate
baseline separation for the peaks of interest.
10.2.3 Inject the appropriate series of calibration standards,
starting with the lowest concentration standard first both before and
after injection of the quality control check sample, reagent blanks,
and field samples. This allows compensation for any instrument drift
occurring during sample analysis. The values from duplicate injections
of these calibration samples should agree within 5 percent of their
mean for the analysis to be valid.
10.2.4 Determine the peak areas, or heights, for the standards and
plot individual values versus halide ion concentrations in g/
ml.
10.2.5 Draw a smooth curve through the points. Use linear
regression to calculate a formula describing the resulting linear
curve.

11.0 Analytical Procedures

11.1 Sample Analysis.
11.1.1 The IC conditions will depend upon analytical column type
and whether suppressed or non-

[[Page 62088]]

suppressed IC is used. An example chromatogram from a non-suppressed
system using a 150-mm Hamilton PRP-X100 anion column, a 2 ml/min flow
rate of a 4 mM 4-hydroxy benzoate solution adjusted to a pH of 8.6
using 1 N NaOH, a 50 l sample loop, and a conductivity
detector set on 1.0 S full scale is shown in Figure 26-2.
11.1.2 Before sample analysis, establish a stable baseline. Next,
inject a sample of water, and determine if any Cl-,
Br-, or F- appears in the chromatogram. If any of
these ions are present, repeat the load/injection procedure until they
are no longer present. Analysis of the acid and alkaline absorbing
solution samples requires separate standard calibration curves; prepare
each according to Section 10.2. Ensure adequate baseline separation of
the analyses.
11.1.3 Between injections of the appropriate series of calibration
standards, inject in duplicate the reagent blanks, quality control
sample, and the field samples. Measure the areas or heights of the
Cl-, Br-, and F- peaks. Use the mean
response of the duplicate injections to determine the concentrations of
the field samples and reagent blanks using the linear calibration
curve. The values from duplicate injections should agree within 5
percent of their mean for the analysis to be valid. If the values of
duplicate injections are not within 5 percent of the mean, the
duplicate injections shall be repeated and all four values used to
determine the average response. Dilute any sample and the blank with
equal volumes of water if the concentration exceeds that of the highest
standard.
11.2 Audit Sample Analysis.
11.2.1 When the method is used to analyze samples to demonstrate
compliance with a source emission regulation, a set of two EPA audit
samples must be analyzed, subject to availability.
11.2.2 Concurrently analyze the audit samples and the compliance
samples in the same manner to evaluate the technique of the analyst and
the standards preparation.
11.2.3 The same analyst, analytical reagents, and analytical
system shall be used for the compliance samples and the EPA audit
samples. If this condition is met, duplicate auditing of subsequent
compliance analyses for the same enforcement agency within a 30-day
period is waived. An audit sample set may not be used to validate
different sets of compliance samples under the jurisdiction of separate
enforcement agencies, unless prior arrangements have been made with
both enforcement agencies.
11.3 Audit Sample Results.
11.3.1 Calculate the concentrations in mg/L of audit sample and
submit results following the instructions provided with the audit
samples.
11.3.2 Report the results of the audit samples and the compliance
determination samples along with their identification numbers, and the
analyst's name to the responsible enforcement authority. Include this
information with reports of any subsequent compliance analyses for the
same enforcement authority during the 30-day period.
11.3.3 The concentrations of the audit samples obtained by the
analyst shall agree within 10 percent of the actual concentrations. If
the 10 percent specification is not met, reanalyze the compliance and
audit samples, and include initial and reanalysis values in the test
report.
11.3.4 Failure to meet the 10 percent specification may require
retests until the audit problems are resolved. However, if the audit
results do not affect the compliance or noncompliance status of the
affected facility, the Administrator may waive the reanalysis
requirement, further audits, or retests and accept the results of the
compliance test. While steps are being taken to resolve audit analysis
problems, the Administrator may also choose to use the data to
determine the compliance or noncompliance status of the affected
facility.

12.0 Data Analysis and Calculations

Note: Retain at least one extra decimal figure beyond those
contained in the available data in intermediate calculations, and
round off only the final answer appropriately.

12.1 Nomenclature.

BX-=Mass concentration of applicable absorbing
solution blank, g halide ion (Cl-, Br-,
F-) /ml, not to exceed 1 g/ml which is 10 times the
published analytical detection limit of 0.1 g/ml.
C=Concentration of hydrogen halide (HX) or halogen (X2), dry
basis, mg/dscm.
K = 10-3 mg/g.
KHCl = 1.028 (g HCl/g-mole)/(g
Cl-/g-mole).
KHBr = 1.013 (g HBr/g-mole)/(g
Br-/g-mole).
KHF = 1.053 (g HF/g-mole)/(g
F-/g-mole).
mHX = Mass of HCl, HBr, or HF in sample, g.
mX2 = Mass of Cl2 or Br2 in sample,
g.
SX- = Analysis of sample, g halide ion
(Cl-, Br-, F-)/ml.
Vm(std)= Dry gas volume measured by the dry gas meter,
corrected to standard conditions, dscm.
Vs = Volume of filtered and diluted sample, ml.

12.2 Calculate the exact Cl-, Br-, and
F- concentration in the halide salt stock standard solutions
using the following equations.
[GRAPHIC] [TIFF OMITTED] TR17OC00.413

12.3 Sample Volume, Dry Basis, Corrected to Standard Conditions.
Calculate the sample volume using Eq. 6-1 of Method 6.
12.4 Total g HCl, HBr, or HF Per Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.414

12.5 Total g Cl2 or Br2 Per Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.415

[[Page 62089]]

12.6 Concentration of Hydrogen Halide or Halogen in Flue Gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.416

13.0 Method Performance

13.1 Precision and Bias. The within-laboratory relative standard
deviations are 6.2 and 3.2 percent at HCl concentrations of 3.9 and
15.3 ppm, respectively. The method does not exhibit a bias to
Cl2 when sampling at concentrations less than 50 ppm.
13.2 Sample Stability. The collected Cl-samples can be
stored for up to 4 weeks.
13.3 Detection Limit. A typical IC instrumental detection limit
for Cl- is 0.2 g/ml. Detection limits for the other
analyses should be similar. Assuming 50 ml liquid recovered from both
the acidified impingers, and the basic impingers, and 0.06 dscm of
stack gas sampled, then the analytical detection limit in the stack gas
would be about 0.1 ppm for HCl and Cl2, respectively.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Steinsberger, S. C. and J. H. Margeson, ``Laboratory and
Field Evaluation of a Methodology for Determination of Hydrogen
Chloride Emissions from Municipal and Hazardous Waste
Incinerators,'' U.S. Environmental Protection Agency, Office of
Research and Development, Report No. 600/3-89/064, April 1989.
Available from the National Technical Information Service,
Springfield, VA 22161 as PB89220586/AS.
2. State of California, Air Resources Board, Method 421,
``Determination of Hydrochloric Acid Emissions from Stationary
Sources,'' March 18, 1987.
3. Cheney, J.L. and C.R. Fortune. Improvements in the
Methodology for Measuring Hydrochloric Acid in Combustion Source
Emissions. J. Environ. Sci. Health. A19(3): 337-350. 1984.
4. Stern, D. A., B. M. Myatt, J. F. Lachowski, and K. T.
McGregor. Speciation of Halogen and Hydrogen Halide Compounds in
Gaseous Emissions. In: Incineration and Treatment of Hazardous
Waste: Proceedings of the 9th Annual Research Symposium, Cincinnati,
Ohio, May 2-4, 1983. Publication No. 600/9-84-015. July 1984.
Available from National Technical Information Service, Springfield,
VA 22161 as PB84-234525.
5. Holm, R. D. and S. A. Barksdale. Analysis of Anions in
Combustion Products. In: Ion Chromatographic Analysis of
Environmental Pollutants. E. Sawicki, J. D. Mulik, and E.
Wittgenstein (eds.). Ann Arbor, Michigan, Ann Arbor Science
Publishers. 1978. pp. 99-110.

BILLING CODE 6560-50-P

[[Page 62090]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.417

[[Page 62091]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.418

BILLING CODE 6560-50-C

Method 26A--Determination of Hydrogen Halide and Halogen Emissions
From Stationary Sources Isokinetic Method

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 2, Method 5, and Method 26.

1.0 Scope and Application

1.1 Analytes.

1.2 This method is applicable for determining emissions of
hydrogen halides (HX) [HCl, HBr, and HF] and halogens (X2)
[Cl2 and Br2] from stationary sources when
specified by the applicable subpart. This method collects the emission
sample isokinetically and is therefore particularly suited for sampling
at sources, such as those controlled by wet scrubbers, emitting acid
particulate matter (e.g., hydrogen halides dissolved in water
droplets).
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 Principle. Gaseous and particulate pollutants are withdrawn
isokinetically from the source and collected in an optional cyclone, on
a filter, and in absorbing solutions. The cyclone collects any liquid
droplets and is not necessary if the source emissions do not contain
them; however, it is preferable to include the cyclone in the sampling
train to protect the filter from any liquid present. The filter
collects particulate matter including halide salts but is not routinely
recovered or analyzed. Acidic and alkaline absorbing solutions collect
the gaseous hydrogen halides and halogens, respectively. Following
sampling of emissions containing liquid droplets, any halides/halogens
dissolved in the liquid in the cyclone and on the filter are vaporized
to gas and collected in the impingers by pulling conditioned ambient
air through the sampling train. The hydrogen halides are solubilized in
the acidic solution and form chloride (Cl-), bromide
(Br-), and fluoride (F-) ions. The halogens have
a very low solubility in the acidic solution and pass through to the
alkaline solution where they are hydrolyzed to form a proton
(H+), the halide ion, and the hypohalous acid (HClO or
HBrO). Sodium thiosulfate is added to the alkaline solution to assure
reaction with the hypohalous acid to form a second halide ion such that
2 halide ions are formed for each molecule of halogen gas. The halide
ions in the separate solutions are measured by ion chromatography (IC).
If desired, the particulate matter recovered

[[Page 62092]]

from the filter and the probe is analyzed following the procedures in
Method 5.

Note: If the tester intends to use this sampling arrangement to
sample concurrently for particulate matter, the alternative Teflon
probe liner, cyclone, and filter holder should not be used. The
Teflon filter support must be used. The tester must also meet the
probe and filter temperature requirements of both sampling trains.

3.0 Definitions. [Reserved]

4.0 Interferences

4.1 Volatile materials, such as chlorine dioxide (ClO2)
and ammonium chloride (NH4Cl), which produce halide ions
upon dissolution during sampling are potential interferents.
Interferents for the halide measurements are the halogen gases which
disproportionate to a hydrogen halide and an hypohalous acid upon
dissolution in water. The use of acidic rather than neutral or basic
solutions for collection of the hydrogen halides greatly reduces the
dissolution of any halogens passing through this solution.
4.2 The simultaneous presence of both HBr and Cl2 may
cause a positive bias in the HCl result with a corresponding negative
bias in the Cl2 result as well as affecting the HBr/
Br2 split.
4.3 High concentrations of nitrogen oxides (NOX) may
produce sufficient nitrate (NO3-) to interfere
with measurements of very low Br-levels.
4.4 There is anecdotal evidence that HF may be outgassed from new
Teflon components. If HF is a target analyte then preconditioning of
new Teflon components, by heating, should be considered.

5.0 Safety

6.0. Equipment and Supplies

Note: Mention of trade names or specific products does not
constitute endorsement by the Environmental Protection Agency.

6.1 Sampling. The sampling train is shown in Figure 26A-1; the
apparatus is similar to the Method 5 train where noted as follows:
6.1.1 Probe Nozzle. Borosilicate or quartz glass; constructed and
calibrated according to Method 5, Sections 6.1.1.1 and 10.1, and
coupled to the probe liner using a Teflon union; a stainless steel nut
is recommended for this union. When the stack temperature exceeds 210
deg.C (410 deg.F), a one-piece glass nozzle/liner assembly must be
used.
6.1.2 Probe Liner. Same as Method 5, Section 6.1.1.2, except metal
liners shall not be used. Water-cooling of the stainless steel sheath
is recommended at temperatures exceeding 500 deg.C (932 deg.F).
Teflon may be used in limited applications where the minimum stack
temperature exceeds 120 deg.C (250 deg.F) but never exceeds the
temperature where Teflon is estimated to become unstable [approximately
210 deg.C (410 deg.F)].
6.1.3 Pitot Tube, Differential Pressure Gauge, Filter Heating
System, Metering System, Barometer, Gas Density Determination
Equipment. Same as Method 5, Sections 6.1.1.3, 6.1.1.4, 6.1.1.6,
6.1.1.9, 6.1.2, and 6.1.3.
6.1.4 Cyclone (Optional). Glass or Teflon. Use of the cyclone is
required only when the sample gas stream is saturated with moisture;
however, the cyclone is recommended to protect the filter from any
liquid droplets present.
6.1.5 Filter Holder. Borosilicate or quartz glass, or Teflon
filter holder, with a Teflon filter support and a sealing gasket. The
sealing gasket shall be constructed of Teflon or equivalent materials.
The holder design shall provide a positive seal against leakage at any
point along the filter circumference. The holder shall be attached
immediately to the outlet of the cyclone.
6.1.6 Impinger Train. The following system shall be used to
determine the stack gas moisture content and to collect the hydrogen
halides and halogens: five or six impingers connected in series with
leak-free ground glass fittings or any similar leak-free
noncontaminating fittings. The first impinger shown in Figure 26A-1
(knockout or condensate impinger) is optional and is recommended as a
water knockout trap for use under high moisture conditions. If used,
this impinger should be constructed as described below for the alkaline
impingers, but with a shortened stem, and should contain 50 ml of 0.1 N
H2SO4. The following two impingers (acid
impingers which each contain 100 ml of 0.1 N
H2SO4) shall be of the Greenburg-Smith design
with the standard tip (Method 5, Section 6.1.1.8). The next two
impingers (alkaline impingers which each contain 100 ml of 0.1 N NaOH)
and the last impinger (containing silica gel) shall be of the modified
Greenburg-Smith design (Method 5, Section 6.1.1.8). The condensate,
acid, and alkaline impingers shall contain known quantities of the
appropriate absorbing reagents. The last impinger shall contain a known
weight of silica gel or equivalent desiccant. Teflon impingers are an
acceptable alternative.
6.1.7 Heating System. Any heating system capable of maintaining a
temperature around the probe and filter holder greater than 120 deg.C
(248 deg.F) during sampling, or such other temperature as specified by
an applicable subpart of the standards or approved by the Administrator
for a particular application.
6.1.8 Ambient Air Conditioning Tube (Optional). Tube tightly
packed with approximately 150 g of fresh 8 to 20 mesh sodium hydroxide-
coated silica, or equivalent, (Ascarite II has been found suitable) to
dry and remove acid gases from the ambient air used to remove moisture
from the filter and cyclone, when the cyclone is used. The inlet and
outlet ends of the tube should be packed with at least 1-cm thickness
of glass wool or filter material suitable to prevent escape of fines.
Fit one end with flexible tubing, etc. to allow connection to probe
nozzle following the test run.
6.2 Sample Recovery.
6.2.1 Probe-Liner and Probe-Nozzle Brushes, Wash Bottles, Glass
Sample Storage Containers, Petri Dishes, Graduated Cylinder and/or
Balance, and Rubber Policeman. Same as Method 5, Sections 6.2.1, 6.2.2,
6.2.3, 6.2.4, 6.2.5, and 6.2.7.
6.2.2 Plastic Storage Containers. Screw-cap polypropylene or
polyethylene containers to store silica gel. High-density polyethylene
bottles with Teflon screw cap liners to store impinger reagents, 1-
liter.

[[Continued on page 62093]]

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

[[pp. 62043-62092]] Amendments for Testing and Monitoring Provisions

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