Appendix A-8 to Part 60--Test Methods 26 through 29

Method 26--Determination of Hydrogen Chloride Emissions From Stationary
Sources
Method 26A--Determination of hydrogen halide and halogen emissions from
stationary sources--isokinetic method

[[Page 549]]

Method 27--Determination of vapor tightness of gasoline delivery tank
using pressure-vacuum test
Method 28--Certification and auditing of wood heaters
Method 28A--Measurement of air to fuel ratio and minimum achievable burn
rates for wood-fired appliances
Method 29--Determination of metals emissions from stationary sources
The test methods in this appendix are referred to in Sec. 60.8
(Performance Tests) and Sec. 60.11 (Compliance With Standards and
Maintenance Requirements) of 40 CFR part 60, subpart A (General
Provisions). Specific uses of these test methods are described in the
standards of performance contained in the subparts, beginning with
Subpart D.
Within each standard of performance, a section title ``Test Methods
and Procedures'' is provided to: (1) Identify the test methods to be
used as reference methods to the facility subject to the respective
standard and (2) identify any special instructions or conditions to be
followed when applying a method to the respective facility. Such
instructions (for example, establish sampling rates, volumes, or
temperatures) are to be used either in addition to, or as a substitute
for procedures in a test method. Similarly, for sources subject to
emission monitoring requirements, specific instructions pertaining to
any use of a test method as a reference method are provided in the
subpart or in Appendix B.
Inclusion of methods in this appendix is not intended as an
endorsement or denial of their applicability to sources that are not
subject to standards of performance. The methods are potentially
applicable to other sources; however, applicability should be confirmed
by careful and appropriate evaluation of the conditions prevalent at
such sources.
The approach followed in the formulation of the test methods
involves specifications for equipment, procedures, and performance. In
concept, a performance specification approach would be preferable in all
methods because this allows the greatest flexibility to the user. In
practice, however, this approach is impractical in most cases because
performance specifications cannot be established. Most of the methods
described herein, therefore, involve specific equipment specifications
and procedures, and only a few methods in this appendix rely on
performance criteria.
Minor changes in the test methods should not necessarily affect the
validity of the results and it is recognized that alternative and
equivalent methods exist. Section 60.8 provides authority for the
Administrator to specify or approve (1) equivalent methods, (2)
alternative methods, and (3) minor changes in the methodology of the
test methods. It should be clearly understood that unless otherwise
identified all such methods and changes must have prior approval of the
Administrator. An owner employing such methods or deviations from the
test methods without obtaining prior approval does so at the risk of
subsequent disapproval and retesting with approved methods.
Within the test methods, certain specific equipment or procedures
are recognized as being acceptable or potentially acceptable and are
specifically identified in the methods. The items identified as
acceptable options may be used without approval but must be identified
in the test report. The potentially approvable options are cited as
``subject to the approval of the Administrator'' or as ``or
equivalent.'' Such potentially approvable techniques or alternatives may
be used at the discretion of the owner without prior approval. However,
detailed descriptions for applying these potentially approvable
techniques or alternatives are not provided in the test methods. Also,
the potentially approvable options are not necessarily acceptable in all
applications. Therefore, an owner electing to use such potentially
approvable techniques or alternatives is responsible for: (1) assuring
that the techniques or alternatives are in fact applicable and are
properly executed; (2) including a written description of the
alternative method in the test report (the written method must be clear
and must be capable of being performed without additional instruction,
and the degree of detail should be similar to the detail contained in
the test methods); and (3) providing any rationale or supporting data
necessary to show the validity of the alternative in the particular
application. Failure to meet these requirements can result in the
Administrator's disapproval of the alternative.

Method 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.

[[Page 550]]

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

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

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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 ft\3\/min).
6.1.9 Purge Pump, Purge Line, Drying Tube, Needle Valve, and Rate
Meter. Pump capable of purging the 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 ft\3\/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.

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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
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

[[Page 553]]

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 [micro]g/ml.
10.2.5 Draw a smooth curve through the points. Use linear regression
to calculate a

[[Page 554]]

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-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 [micro]l sample loop, and a
conductivity detector set on 1.0 [micro]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, [micro]g halide ion (Cl^-, Br^-,
F^-) /ml, not to exceed 1 [micro]g/ml which is 10 times the
published analytical detection limit of 0.1 [micro]g/ml.
C=Concentration of hydrogen halide (HX) or halogen (X2), dry
basis, mg/dscm.
K=10^-3 mg/[micro]g.
KHCl=1.028 ([micro]g HCl/[micro]g-mole)/([micro]g
Cl^-/[micro]g-mole).
KHBr=1.013 ([micro]g HBr/[micro]g-mole)/([micro]g
Br^-/[micro]g-mole).
KHF=1.053 ([micro]g HF/[micro]g-mole)/([micro]g
F^-/[micro]g-mole).
mHX=Mass of HCl, HBr, or HF in sample, [micro]g.
mX2=Mass of Cl2 or Br2 in sample,
[micro]g.
SX^-=Analysis of sample, [micro]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.

[[Page 555]]

[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 [micro]g HCl, HBr, or HF Per Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.414

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

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 [micro]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.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 556]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.417

[[Page 557]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.418

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^-),

[[Page 558]]

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 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 a 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

[[Page 559]]

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.
6.2.3 Funnels. Glass or high-density polyethylene, to aid in sample
recovery.
6.3 Sample Preparation and Analysis.
6.3.1 Volumetric Flasks. Class A, various sizes.
6.3.2 Volumetric Pipettes. Class A, assortment. To dilute samples to
calibration range of the ion chromatograph (IC).
6.3.3 Ion Chromatograph (IC). Suppressed or nonsuppressed, with a
conductivity detector and electronic integrator operating in the peak
area mode. Other detectors, a strip chart recorder, and peak heights may
be used.

7.0 Reagents and Standards

7.1 Sampling.
7.1.1 Filter. Teflon mat (e.g., Pallflex TX40HI45) filter. When the
stack gas temperature exceeds 210 [deg]C (410 [deg]F) a quartz fiber
filter may be used.
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 1 L, slowly add 2.80 ml of
concentrated 17.9 M H2SO4 to about 900 ml of water while stirring, and
adjust the final volume to 1 L using additional water. Shake well to mix
the solution.
7.1.4 Silica Gel, Crushed Ice, and Stopcock Grease. Same as Method
5, Sections 7.1.2, 7.1.4, and 7.1.5, respectively.
7.1.5 Alkaline Absorbing Solution, 0.1 N Sodium Hydroxide (NaOH). To
prepare 1 L, dissolve 4.00 g of solid NaOH in about 900 ml of water and
adjust the final volume to 1 L using additional water. Shake well to mix
the solution.
7.1.6 Sodium Thiosulfate,
(Na2S2O33.5 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 200 ml of each absorbing solution (250 ml of the acidic
absorbing solution, if a condensate impinger is used) to the same final
volume as the field samples using the blank sample of rinse water. If a
particulate determination is conducted, collect a blank sample of
acetone.
7.2.3 Halide Salt Stock Standard Solutions. Prepare concentrated
stock solutions from reagent grade sodium chloride (NaCl), sodium
bromide (NaBr), and sodium fluoride

[[Page 560]]

(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 26A-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 26A-2 and 26A-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. Same as Method 26, Section 7.2.4.
7.2.5 Water. Same as Section 7.1.1.
7.2.6 Acetone. Same as Method 5, Section 7.2.
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 analysts
should be trained and experienced with the procedures to ensure reliable
results.

8.1 Sampling.
8.1.1 Pretest Preparation. Follow the general procedure given in
Method 5, Section 8.1, except the filter need only be desiccated and
weighed if a particulate determination will be conducted.
8.1.2 Preliminary Determinations. Same as Method 5, Section 8.2.
8.1.3 Preparation of Sampling Train. Follow the general procedure
given in Method 5, Section 8.1.3, except for the following variations:
Add 50 ml of 0.1 N H2SO4 to the condensate
impinger, if used. Place 100 ml of 0.1 N H2SO4 in
each of the next two impingers. Place 100 ml of 0.1 N NaOH in each of
the following two impingers. Finally, transfer approximately 200-300 g
of preweighed silica gel from its container to the last impinger. Set up
the train as in Figure 26A-1. When used, the optional cyclone is
inserted between the probe liner and filter holder and located in the
heated filter box.
8.1.4 Leak-Check Procedures. Follow the leak-check procedures given
in Method 5, Sections 8.4.2 (Pretest Leak-Check), 8.4.3 (Leak-Checks
During the Sample Run), and 8.4.4 (Post-Test Leak-Check).
8.1.5 Sampling Train Operation. Follow the general procedure given
in Method 5, Section 8.5. It is important to maintain a temperature
around the probe, filter (and cyclone, if used) 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 these emissions. The applicable subparts may
specify alternative higher temperatures.) For each run, record the data
required on a data sheet such as the one shown in Method 5, Figure 5-3.
If the condensate impinger becomes too full, it may be emptied,
recharged with 50 ml of 0.1 N H2SO4, and replaced
during the sample run. The condensate emptied must be saved and included
in the measurement of the volume of moisture collected and included in
the sample for analysis. The additional 50 ml of absorbing reagent must
also be considered in calculating the moisture. Before the sampling
train integrity is compromised by removing the impinger, conduct a leak-
check as described in Method 5, Section 8.4.2.
8.1.6 Post-Test Moisture Removal (Optional). When the optional
cyclone is included in the sampling train or when liquid is visible on
the filter at the end of a sample run even in the absence of a cyclone,
perform the following procedure. Upon completion of the test run,
connect the ambient air conditioning tube at the probe inlet and operate
the train with the filter heating system at least 120 [deg]C (248
[deg]F) at a low flow rate (e.g., [Delta]H=1 in. H2O) to
vaporize any liquid and hydrogen halides in the cyclone or on the filter
and pull them through the train into the impingers. After 30 minutes,
turn off the flow, remove the conditioning tube, and examine the cyclone
and filter for any visible liquid. If liquid is visible, repeat this
step for 15 minutes and observe again. Keep repeating until the cyclone
is dry.

Note: It is critical that this is repeated until the cyclone is
completely dry.

8.2 Sample Recovery. Allow the probe to cool. When the probe can be
handled safely, wipe off all the external surfaces of the tip of the
probe nozzle and place a cap loosely over the tip to prevent gaining or
losing particulate matter. Do not cap the probe tip tightly while the
sampling train is cooling down because this will create a vacuum in the
filter holder, drawing water from the impingers into the holder. Before
moving the sampling train to the cleanup site, remove the probe from the
sample train, wipe off any silicone grease, and cap the open outlet of
the impinger train, being careful not to lose any condensate that might
be present. Wipe off

[[Page 561]]

any silicone grease and cap the filter or cyclone inlet. Remove the
umbilical cord from the last impinger and cap the impinger. If a
flexible line is used between the first impinger and the filter holder,
disconnect it at the filter holder and let any condensed water drain
into the first impinger. Wipe off any silicone grease and cap the filter
holder outlet and the impinger inlet. Ground glass stoppers, plastic
caps, serum caps, Teflon tape, Parafilm, or aluminum foil may be used to
close these openings. Transfer the probe and filter/impinger assembly to
the cleanup area. This area should be clean and protected from the
weather to minimize sample contamination or loss. Inspect the train
prior to and during disassembly and note any abnormal conditions. Treat
samples as follows:
8.2.1 Container No. 1 (Optional; Filter Catch for Particulate
Determination). Same as Method 5, Section 8.7.6.1, Container No. 1.
8.2.2 Container No. 2 (Optional; Front-Half Rinse for Particulate
Determination). Same as Method 5, Section 8.7.6.2, Container No. 2.
8.2.3 Container No. 3 (Knockout and Acid Impinger Catch for Moisture
and Hydrogen Halide Determination). Disconnect the impingers. Measure
the liquid in the acid and knockout impingers to 1
ml by using a graduated cylinder or by weighing it to 0.5 g by using a balance. Record the volume or weight of
liquid present. This information is required to calculate the moisture
content of the effluent gas. Quantitatively transfer this liquid to a
leak-free sample storage container. Rinse these impingers and connecting
glassware including the back portion of the filter holder (and flexible
tubing, if used) with water and add these rinses to the storage
container. Seal the container, shake to mix, and label. The fluid level
should be marked so that if any sample is lost during transport, a
correction proportional to the lost volume can be applied. Retain rinse
water and acidic absorbing solution blanks to be analyzed with the
samples.
8.2.4 Container No. 4 (Alkaline Impinger Catch for Halogen and
Moisture Determination). Measure and record the liquid in the alkaline
impingers as described in Section 8.2.3. Quantitatively transfer this
liquid to a leak-free sample storage container. Rinse these two
impingers and connecting glassware with water and add these rinses to
the container. Add 25 mg of sodium thiosulfate per ppm halogen
anticipated to be in the stack gas multiplied by the volume (dscm) of
stack gas sampled (0.7 mg/ppm-dscf). Seal the container, shake to mix,
and label; mark the fluid level. Retain alkaline absorbing solution
blank to be analyzed with the samples.

Note: 25 mg per sodium thiosulfate per ppm halogen anticipated to be
in the stack 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.

8.2.5 Container No. 5 (Silica Gel for Moisture Determination). Same
as Method 5, Section 8.7.6.3, Container No. 3.
8.2.6 Container Nos. 6 through 9 (Reagent Blanks). Save portions of
the absorbing reagents (0.1 N H2SO4 and 0.1 N
NaOH) equivalent to the amount used in the sampling train; dilute to the
approximate volume of the corresponding samples using rinse water
directly from the wash bottle being used. Add the same ratio of sodium
thiosulfate solution used in container No. 4 to the 0.1 N NaOH absorbing
reagent blank. Also, save a portion of the rinse water alone and a
portion of the acetone equivalent to the amount used to rinse the front
half of the sampling train. Place each in a separate, prelabeled sample
container.
8.2.7 Prior to shipment, recheck all sample containers to ensure
that the caps are well-secured. Seal the lids of all containers around
the circumference with Teflon tape. Ship all liquid samples upright and
all particulate filters with the particulate catch facing upward.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.1.4, 10.1................... Sampling Ensure accurate
equipment leak- measurement of stack
check and gas flow rate,
calibration. sample volume.
11.5.......................... Audit sample Evaluate analyst's
analysis. technique and
standards
preparation.
------------------------------------------------------------------------

9.1 Volume Metering System Checks. Same as Method 5, Section 9.2.

10.0 Calibration and Standardization

Note: Maintain a laboratory log of all calibrations.

10.1 Probe Nozzle, Pitot Tube Assembly, Dry Gas Metering System,
Probe Heater, Temperature Sensors, Leak-Check of Metering System, and
Barometer. Same as Method 5, Sections 10.1, 10.2, 10.3, 10.4, 10.5,
8.4.1, and 10.6, respectively.
10.2 Ion Chromatograph.

[[Page 562]]

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 three 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 height, of the standards and
plot individual values versus halide ion concentrations in [micro]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

Note: the liquid levels in the sample containers 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.

11.1 Sample Analysis.
11.1.1 The IC conditions will depend upon analytical column type and
whether suppressed or non-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 [micro]l sample loop, and a
conductivity detector set on 1.0 [micro]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 duplicator
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 Container Nos. 1 and 2 and Acetone Blank (Optional; Particulate
Determination). Same as Method 5, Sections 11.2.1 and 11.2.2,
respectively.
11.3 Container No. 5. Same as Method 5, Section 11.2.3 for silica
gel.
11.4 Audit Sample Analysis.
11.4.1 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.
11.4.2 Concurrently analyze the audit samples and the compliance
samples in the same manner to evaluate the technique of the analyst and
the standards preparation.
11.4.3 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.
11.5 Audit Sample Results.
11.5.1 Calculate the concentrations in mg/L of audit sample and
submit results following the instructions provided with the audit
samples.
11.5.2 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.
11.5.3 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.
11.5.4 Failure to meet the 10 percent specification may require
retests until the audit problems are resolved. However, if the audit

[[Page 563]]

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. Same as Method 5, Section 12.1. In addition:

BX-=Mass concentration of applicable absorbing solution
blank, [micro]g halide ion (Cl^-, Br^-,
F^-)/ml, not to exceed 1 [micro]g/ml which is 10 times the
published analytical detection limit of 0.1 [micro]g/ml. (It is also
approximately 5 percent of the mass concentration anticipated to result
from a one hour sample at 10 ppmv HCl.)
C=Concentration of hydrogen halide (HX) or halogen (X2), dry
basis, mg/dscm.
K=10^-3 mg/[micro]g.
KHCl=1.028 ([micro]g HCl/[micro]g-mole)/([micro]g
Cl^-/[micro]g-mole).
KHBr=1.013 ([micro]g HBr/[micro]g-mole)/([micro]g
Br^-/[micro]g-mole).
KHF=1.053 ([micro]g HF/[micro]g-mole)/([micro]g
F^-/[micro]g-mole).
mHX=Mass of HCl, HBr, or HF in sample, ug.
mX2=Mass of Cl2 or Br2 in sample, ug.
SX-=Analysis of sample, ug halide ion (Cl^-,
Br^-, F^-)/ml.
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] TR17OC00.419

[GRAPHIC] [TIFF OMITTED] TR17OC00.420

12.3 Average Dry Gas Meter Temperature and Average Orifice Pressure
Drop. See data sheet (Figure 5-3 of Method 5).
12.4 Dry Gas Volume. Calculate Vm(std) and adjust for
leakage, if necessary, using the equation in Section 12.3 of Method 5.
12.5 Volume of Water Vapor and Moisture Content. Calculate the
volume of water vapor Vw(std) and moisture content
Bws from the data obtained in this method (Figure 5-3 of
Method 5); use Equations 5-2 and 5-3 of Method 5.
12.6 Isokinetic Variation and Acceptable Results. Use Method 5,
Section 12.11.
12.7 Acetone Blank Concentration, Acetone Wash Blank Residue Weight,
Particulate Weight, and Particulate Concentration. For particulate
determination.
12.8 Total [micro]g HCl, HBr, or HF Per Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.421

12.9 Total [micro]g Cl2 or Br2 Per Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.422

12.10 Concentration of Hydrogen Halide or Halogen in Flue Gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.423

12.11 Stack Gas Velocity and Volumetric Flow Rate. Calculate the
average stack gas velocity and volumetric flow rate, if needed, using
data obtained in this method and the equations in Sections 12.3 and 12.4
of Method 2.

13.0 Method Performance

13.1 Precision and Bias. The method has a possible measurable
negative bias below 20 ppm HCl perhaps due to reaction with small
amounts of moisture in the probe and filter. Similar bias for the other
hydrogen halides is possible.
13.2 Sample Stability. The collected Cl-samples can be stored for up
to 4 weeks for analysis for HCl and Cl2.
13.3 Detection Limit. A typical analytical detection limit for HCl
is 0.2 [micro]g/ml. Detection limits for the other analyses should be
similar. Assuming 300 ml of liquid recovered for the acidified impingers
and a similar

[[Page 564]]

amounts recovered from the basic impingers, and 1 dscm of stack gas
sampled, the analytical detection limits in the stack gas would be about
0.04 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.
Publication No. 600/3-89/064. April 1989. Available from 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.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 565]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.424

Method 27--Determination of Vapor Tightness of Gasoline Delivery Tank
Using Pressure Vaccuum Test

1.0 Scope and Application

1.1 Applicability. This method is applicable for the determination
of vapor tightness of a gasoline delivery collection equipment.

2.0 Summary of Method

2.1 Pressure and vacuum are applied alternately to the compartments
of a gasoline delivery tank and the change in pressure or vacuum is
recorded after a specified period of time.

[[Page 566]]

3.0 Definitions

3.1 Allowable pressure change ([Delta]p) means the allowable amount
of decrease in pressure during the static pressure test, within the time
period t, as specified in the appropriate regulation, in mm
H2O.
3.2 Allowable vacuum change ([Delta]v) means the allowable amount of
decrease in vacuum during the static vacuum test, within the time period
t, as specified in the appropriate regulation, in mm H2O.
3.3 Compartment means a liquid-tight division of a delivery tank.
3.4 Delivery tank means a container, including associated pipes and
fittings, that is attached to or forms a part of any truck, trailer, or
railcar used for the transport of gasoline.
3.5 Delivery tank vapor collection equipment means any piping,
hoses, and devices on the delivery tank used to collect and route
gasoline vapors either from the tank to a bulk terminal vapor control
system or from a bulk plant or service station into the tank.
3.6 Gasoline means a petroleum distillate or petroleum distillate/
alcohol blend having a Reid vapor pressure of 27.6 kilopascals or
greater which is used as a fuel for internal combustion engines.
3.7 Initial pressure (Pi) means the pressure applied to the delivery
tank at the beginning of the static pressure test, as specified in the
appropriate regulation, in mm H2O.
3.8 Initial vacuum (Vi) means the vacuum applied to the delivery
tank at the beginning of the static vacuum test, as specified in the
appropriate regulation, in mm H3.
3.9 Time period of the pressure or vacuum test (t) means the time
period of the test, as specified in the appropriate regulation, during
which the change in pressure or vacuum is monitored, in minutes.

4.0 Interferences [Reserved]

5.0 Safety

5.1 Gasoline contains several volatile organic compounds (e.g.,
benzene and hexane) which presents a potential for fire and/or
explosions. It is advisable to take appropriate precautions when testing
a gasoline vessel's vapor tightness, such as refraining from smoking and
using explosion-proof equipment.
5.2 This method may involve hazardous materials, operations, and
equipment. This test method may not address all of the safety problems
associated with its use. It is the responsibility of the user of this
test method to establish appropriate safety and health practices and
determine the applicability of regulatory limitations prior to
performing this test method

6.0 Equipment and Supplies

The following equipment and supplies are required for testing:
6.1 Pressure Source. Pump or compressed gas cylinder of air or inert
gas sufficient to pressurize the delivery tank to 500 mm (20 in.)
H2O above atmospheric pressure.
6.2 Regulator. Low pressure regulator for controlling pressurization
of the delivery tank.
6.3 Vacuum Source. Vacuum pump capable of evacuating the delivery
tank to 250 mm (10 in.) H2O below atmospheric pressure.
6.4 Pressure-Vacuum Supply Hose.
6.5 Manometer. Liquid manometer, or equivalent instrument, capable
of measuring up to 500 mm (20 in.) H2O gauge pressure with
2.5 mm (0.1 in.) H2O precision.
6.6 Pressure-Vacuum Relief Valves. The test apparatus shall be
equipped with an inline pressure-vacuum relief valve set to activate at
675 mm (26.6 in.) H2O above atmospheric pressure or 250 mm
(10 in.) H2O below atmospheric pressure, with a capacity equal to the
pressurizing or evacuating pumps.
6.7 Test Cap for Vapor Recovery Hose. This cap shall have a tap for
manometer connection and a fitting with shut-off valve for connection to
the pressure-vacuum supply hose.
6.8 Caps for Liquid Delivery Hoses.

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Pretest Preparations.
8.1.1 Summary. Testing problems may occur due to the presence of
volatile vapors and/or temperature fluctuations inside the delivery
tank. Under these conditions, it is often difficult to obtain a stable
initial pressure at the beginning of a test, and erroneous test results
may occur. To help prevent this, it is recommended that prior to
testing, volatile vapors be removed from the tank and the temperature
inside the tank be allowed to stabilize. Because it is not always
possible to completely attain these pretest conditions, a provision to
ensure reproducible results is included. The difference in results for
two consecutive runs must meet the criteria in Sections 8.2.2.5 and
8.2.3.5.
8.1.2 Emptying of Tank. The delivery tank shall be emptied of all
liquid.
8.1.3 Purging of Vapor. As much as possible the delivery tank shall
be purged of all volatile vapors by any safe, acceptable method. One
method is to carry a load of non-volatile liquid fuel, such as diesel or
heating oil, immediately prior to the test, thus flushing out all the
volatile gasoline vapors. A second method is to remove the volatile
vapors by blowing ambient air into each tank compartment for at least 20
minutes. This second method is usually not as effective and

[[Page 567]]

often causes stabilization problems, requiring a much longer time for
stabilization during the testing.
8.1.4 Temperature Stabilization. As much as possible, the test shall
be conducted under isothermal conditions. The temperature of the
delivery tank should be allowed to equilibrate in the test environment.
During the test, the tank should be protected from extreme environmental
and temperature variability, such as direct sunlight.
8.2 Test Procedure.
8.2.1 Preparations.
8.2.1.1 Open and close each dome cover.
8.2.1.2 Connect static electrical ground connections to the tank.
Attach the liquid delivery and vapor return hoses, remove the liquid
delivery elbows, and plug the liquid delivery fittings.

Note: The purpose of testing the liquid delivery hoses is to detect
tears or holes that would allow liquid leakage during a delivery. Liquid
delivery hoses are not considered to be possible sources of vapor
leakage, and thus, do not have to be attached for a vapor leakage test.
Instead, a liquid delivery hose could be either visually inspected, or
filled with water to detect any liquid leakage.

8.2.1.3 Attach the test cap to the end of the vapor recovery hose.
8.2.1.4 Connect the pressure-vacuum supply hose and the pressure-
vacuum relief valve to the shut-off valve. Attach a manometer to the
pressure tap.
8.2.1.5 Connect compartments of the tank internally to each other if
possible. If not possible, each compartment must be tested separately,
as if it were an individual delivery tank.
8.2.2 Pressure Test.
8.2.2.1 Connect the pressure source to the pressure-vacuum supply
hose.
8.2.2.2 Open the shut-off valve in the vapor recovery hose cap.
Apply air pressure slowly, pressurize the tank to Pi, the
initial pressure specified in the regulation.
8.2.2.3 Close the shut-off and allow the pressure in the tank to
stabilize, adjusting the pressure if necessary to maintain pressure of
Pi. When the pressure stabilizes, record the time and initial
pressure.
8.2.2.4 At the end of the time period (t) specified in the
regulation, record the time and final pressure.
8.2.2.5 Repeat steps 8.2.2.2 through 8.2.2.4 until the change in
pressure for two consecutive runs agrees within 12.5 mm (0.5 in.)
H2O. Calculate the arithmetic average of the two results.
8.2.2.6 Compare the average measured change in pressure to the
allowable pressure change, [Delta]p, specified in the regulation. If the
delivery tank does not satisfy the vapor tightness criterion specified
in the regulation, repair the sources of leakage, and repeat the
pressure test until the criterion is met.
8.2.2.7 Disconnect the pressure source from the pressure-vacuum
supply hose, and slowly open the shut-off valve to bring the tank to
atmospheric pressure.
8.2.3 Vacuum Test.
8.2.3.1 Connect the vacuum source to the pressure-vacuum supply
hose.
8.2.3.2 Open the shut-off valve in the vapor recovery hose cap.
Slowly evacuate the tank to Vi, the initial vacuum specified
in the regulation.
8.2.3.3 Close the shut-off valve and allow the pressure in the tank
to stabilize, adjusting the pressure if necessary to maintain a vacuum
of Vi. When the pressure stabilizes, record the time and
initial vacuum.
8.2.3.4 At the end of the time period specified in the regulation
(t), record the time and final vacuum.
8.2.3.5 Repeat steps 8.2.3.2 through 8.2.3.4 until the change in
vacuum for two consecutive runs agrees within 12.5 mm (0.5 in.)
H2O. Calculate the arithmetic average of the two results.
8.2.3.6 Compare the average measured change in vacuum to the
allowable vacuum change, [Delta]v, as specified in the regulation. If
the delivery tank does not satisfy the vapor tightness criterion
specified in the regulation, repair the sources of leakage, and repeat
the vacuum test until the criterion is met.
8.2.3.7 Disconnect the vacuum source from the pressure-vacuum supply
hose, and slowly open the shut-off valve to bring the tank to
atmospheric pressure.
8.2.4 Post-Test Clean-up. Disconnect all test equipment and return
the delivery tank to its pretest condition.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section(s) measure Effect
------------------------------------------------------------------------
8.2.2.5, 8.3.3.5.............. Repeat test Ensures data
procedures until precision.
change in
pressure or
vacuum for two
consecutive runs
agrees within
12.5 mm
(0.5 in.) H2O.
------------------------------------------------------------------------

[[Page 568]]

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedures [Reserved]

12.0 Data Analysis and Calculations [Reserved]

13.0 Method Performance

13.1 Precision. The vapor tightness of a gasoline delivery tank
under positive or negative pressure, as measured by this method, is
precise within 12.5 mm (0.5 in.) H2O
13.2 Bias. No bias has been identified.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

16.1 The pumping of water into the bottom of a delivery tank is an
acceptable alternative to the pressure source described above. Likewise,
the draining of water out of the bottom of a delivery tank may be
substituted for the vacuum source. Note that some of the specific step-
by-step procedures in the method must be altered slightly to accommodate
these different pressure and vacuum sources.
16.2 Techniques other than specified above may be used for purging
and pressurizing a delivery tank, if prior approval is obtained from the
Administrator. Such approval will be based upon demonstrated equivalency
with the above method.

17.0 References [Reserved]

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

Method 28--Certification and Auditing of Wood Heaters

1.0 Scope and Application

1.1 Analyte. Particulate matter (PM). No CAS number assigned.
1.2 Applicability. This method is applicable for the certification
and auditing of wood heaters, including pellet burning wood heaters.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 Particulate matter emissions are measured from a wood heater
burning a prepared test fuel crib in a test facility maintained at a set
of prescribed conditions. Procedures for determining burn rates and
particulate emission rates and for reducing data are provided.

3.0 Definitions

3.1 2 x 4 or 4 x 4 means two inches by four inches or four inches by
four inches (50 mm by 100 mm or 100 mm by 100 mm), as nominal dimensions
for lumber.
3.2 Burn rate means the rate at which test fuel is consumed in a
wood heater. Measured in kilograms or lbs of wood (dry basis) per hour
(kg/hr or lb/hr).
3.3 Certification or audit test means a series of at least four test
runs conducted for certification or audit purposes that meets the burn
rate specifications in Section 8.4.
3.4 Firebox means the chamber in the wood heater in which the test
fuel charge is placed and combusted.
3.5 Height means the vertical distance extending above the loading
door, if fuel could reasonably occupy that space, but not more than 2
inches above the top (peak height) of the loading door, to the floor of
the firebox (i.e., below a permanent grate) if the grate allows a 1-inch
diameter piece of wood to pass through the grate, or, if not, to the top
of the grate. Firebox height is not necessarily uniform but must account
for variations caused by internal baffles, air channels, or other
permanent obstructions.
3.6 Length means the longest horizontal fire chamber dimension that
is parallel to a wall of the chamber.
3.7 Pellet burning wood heater means a wood heater which meets the
following criteria: (1) The manufacturer makes no reference to burning
cord wood in advertising or other literature, (2) the unit is safety
listed for pellet fuel only, (3) the unit operating and instruction
manual must state that the use of cordwood is prohibited by law, and (4)
the unit must be manufactured and sold including the hopper and auger
combination as integral parts.
3.8 Secondary air supply means an air supply that introduces air to
the wood heater such that the burn rate is not altered by more than 25
percent when the secondary air supply is adjusted during the test run.
The wood heater manufacturer can document this through design drawings
that show the secondary air is introduced only into a mixing chamber or
secondary chamber outside the firebox.

[[Page 569]]

3.9 Test facility means the area in which the wood heater is
installed, operated, and sampled for emissions.
3.10 Test fuel charge means the collection of test fuel pieces
placed in the wood heater at the start of the emission test run.
3.11 Test fuel crib means the arrangement of the test fuel charge
with the proper spacing requirements between adjacent fuel pieces.
3.12 Test fuel loading density means the weight of the as-fired test
fuel charge per unit volume of usable firebox.
3.13 Test fuel piece means the 2 x 4 or 4 x 4 wood piece cut to the
length required for the test fuel charge and used to construct the test
fuel crib.
3.14 Test run means an individual emission test which encompasses
the time required to consume the mass of the test fuel charge.
3.15 Usable firebox volume means the volume of the firebox
determined using its height, length, and width as defined in this
section.
3.16 Width means the shortest horizontal fire chamber dimension that
is parallel to a wall of the chamber.
3.17 Wood heater means an enclosed, woodburning appliance capable of
and intended for space heating or domestic water heating, as defined in
the applicable regulation.

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

Same as Section 6.0 of either Method 5G or Method 5H, with the
addition of the following:
6.1 Insulated Solid Pack Chimney. For installation of wood heaters.
Solid pack insulated chimneys shall have a minimum of 2.5 cm (1 in.)
solid pack insulating material surrounding the entire flue and possess a
label demonstrating conformance to U.L. 103 (incorporated by reference--
see Sec. 60.17).
6.2 Platform Scale and Monitor. For monitoring of fuel load weight
change. The scale shall be capable of measuring weight to within 0.05 kg
(0.1 lb) or 1 percent of the initial test fuel charge weight, whichever
is greater.
6.3 Wood Heater Temperature Monitors. Seven, each capable of
measuring temperature to within 1.5 percent of expected absolute
temperatures.
6.4 Test Facility Temperature Monitor. A thermocouple located
centrally in a vertically oriented 150 mm (6 in.) long, 50 mm (2 in.)
diameter pipe shield that is open at both ends, capable of measuring
temperature to within 1.5 percent of expected temperatures.
6.5 Balance (optional). Balance capable of weighing the test fuel
charge to within 0.05 kg (0.1 lb).
6.6 Moisture Meter. Calibrated electrical resistance meter for
measuring test fuel moisture to within 1 percent moisture content.
6.7 Anemometer. Device capable of detecting air velocities less than
0.10 m/sec (20 ft/min), for measuring air velocities near the test
appliance.
6.8 Barometer. Mercury, aneroid or other barometer capable of
measuring atmospheric pressure to within 2.5 mm Hg (0.1 in. Hg).
6.9 Draft Gauge. Electromanometer or other device for the
determination of flue draft or static pressure readable to within 0.50
Pa (0.002 in. H2O).
6.10 Humidity Gauge. Psychrometer or hygrometer for measuring room
humidity.
6.11 Wood Heater Flue.
6.11.1 Steel flue pipe extending to 2.6 0.15 m
(8.5 0.5 ft) above the top of the platform scale,
and above this level, insulated solid pack type chimney extending to 4.6
0.3 m (15 1 ft) above the
platform scale, and of the size specified by the wood heater
manufacturer. This applies to both freestanding and insert type wood
heaters.
6.11.2 Other chimney types (e.g., solid pack insulated pipe) may be
used in place of the steel flue pipe if the wood heater manufacturer's
written appliance specifications require such chimney for home
installation (e.g., zero clearance wood heater inserts). Such
alternative chimney or flue pipe must remain and be sealed with the wood
heater following the certification test.
6.12 Test Facility. The test facility shall meet the following
requirements during testing:
6.12.1 The test facility temperature shall be maintained between 18
and 32 [deg]C (65 and 90 [deg]F) during each test run.
6.12.2 Air velocities within 0.6 m (2 ft) of the test appliance and
exhaust system shall be less than 0.25 m/sec (50 ft/min) without fire in
the unit.
6.12.3 The flue shall discharge into the same space or into a space
freely communicating with the test facility. Any hood or similar device
used to vent combustion products shall not induce a draft greater than
1.25 Pa (0.005 in. H2O) on the wood heater measured when the
wood heater is not operating.
6.12.4 For test facilities with artificially induced barometric
pressures (e.g., pressurized chambers), the barometric pressure in

[[Page 570]]

the test facility shall not exceed 775 mm Hg (30.5 in. Hg) during any
test run.

7.0 Reagents and Standards

Same as Section 6.0 of either Method 5G or Method 5H, with the
addition of the following:
7.1 Test Fuel. The test fuel shall conform to the following
requirements:
7.1.1 Fuel Species. Untreated, air-dried, Douglas fir lumber. Kiln-
dried lumber is not permitted. The lumber shall be certified C grade
(standard) or better Douglas fir by a lumber grader at the mill of
origin as specified in the West Coast Lumber Inspection Bureau Standard
No. 16 (incorporated by reference--see Sec. 60.17).
7.1.2 Fuel Moisture. The test fuel shall have a moisture content
range between 16 to 20 percent on a wet basis (19 to 25 percent dry
basis). Addition of moisture to previously dried wood is not allowed. It
is recommended that the test fuel be stored in a temperature and
humidity-controlled room.
7.1.3 Fuel Temperature. The test fuel shall be at the test facility
temperature of 18 to 32 [deg]C (65 to 90 [deg]F).
7.1.4 Fuel Dimensions. The dimensions of each test fuel piece shall
conform to the nominal measurements of 2x4 and 4x4 lumber. Each piece of
test fuel (not including spacers) shall be of equal length, except as
necessary to meet requirements in Section 8.8, and shall closely
approximate \5/6\ the dimensions of the length of the usable firebox.
The fuel piece dimensions shall be determined in relation to the
appliance's firebox volume according to guidelines listed below:
7.1.4.1 If the usable firebox volume is less than or equal to 0.043
m\3\ (1.5 ft\3\), use 2x4 lumber.
7.1.4.2 If the usable firebox volume is greater than 0.043 m\3\ (1.5
ft\3\) and less than or equal to 0.085 m\3\ (3.0 ft\3\), use 2x4 and 4x4
lumber. About half the weight of the test fuel charge shall be 2x4
lumber, and the remainder shall be 4x4 lumber.
7.1.4.3 If the usable firebox volume is greater than 0.085 m\3\ (3.0
ft\3\), use 4x4 lumber.
7.2 Test Fuel Spacers. Air-dried, Douglas fir lumber meeting the
requirements outlined in Sections 7.1.1 through 7.1.3. The spacers shall
be 130x40x20 mm (5x1.5x0.75 in.).

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Test Run Requirements.
8.1.1 Burn Rate Categories. One emission test run is required in
each of the following burn rate categories:

Burn Rate Categories
[Average kg/hr (lb/hr), dry basis]
----------------------------------------------------------------------------------------------------------------
Category 1 Category 2 Category 3 Category 4
----------------------------------------------------------------------------------------------------------------
<0.80................................ 0.80 to 1.25........... 1.25 to 1.90........... Maximum.
(<1.76).............................. (1.76 to 2.76)......... (2.76 to 4.19)......... burn rate.
----------------------------------------------------------------------------------------------------------------

8.1.1.1 Maximum Burn Rate. For Category 4, the wood heater shall be
operated with the primary air supply inlet controls fully open (or, if
thermostatically controlled, the thermostat shall be set at maximum heat
output) during the entire test run, or the maximum burn rate setting
specified by the manufacturer's written instructions.
8.1.1.2 Other Burn Rate Categories. For burn rates in Categories 1
through 3, the wood heater shall be operated with the primary air supply
inlet control, or other mechanical control device, set at a
predetermined position necessary to obtain the average burn rate
required for the category.
8.1.1.3 Alternative Burn Rates for Burn Rate Categories 1 and 2.
8.1.1.3.1 If a wood heater cannot be operated at a burn rate below
0.80 kg/hr (1.76 lb/hr), two test runs shall be conducted with burn
rates within Category 2. If a wood heater cannot be operated at a burn
rate below 1.25 kg/hr (2.76 lb/hr), the flue shall be dampered or the
air supply otherwise controlled in order to achieve two test runs within
Category 2.
8.1.1.3.2 Evidence that a wood heater cannot be operated at a burn
rate less than 0.80 kg/hr shall include documentation of two or more
attempts to operate the wood heater in burn rate Category 1 and fuel
combustion has stopped, or results of two or more test runs
demonstrating that the burn rates were greater than 0.80 kg/hr when the
air supply controls were adjusted to the lowest possible position or
settings. Stopped fuel combustion is evidenced when an elapsed time of
30 minutes or more has occurred without a measurable (< 0.05 kg (0.1 lb)
or 1.0 percent, whichever is greater) weight change in the test fuel
charge. See also Section 8.8.3. Report the evidence and the reasoning
used to determine that a test in burn rate Category 1 cannot be
achieved; for example, two unsuccessful attempts to operate at a burn
rate of 0.4 kg/hr are not sufficient evidence that burn rate Category 1
cannot be achieved.

Note: After July 1, 1990, if a wood heater cannot be operated at a
burn rate less than 0.80 kg/hr, at least one test run with an average
burn rate of 1.00 kg/hr or less shall be conducted. Additionally, if
flue dampering

[[Page 571]]

must be used to achieve burn rates below 1.25 kg/hr (or 1.0 kg/hr),
results from a test run conducted at burn rates below 0.90 kg/hr need
not be reported or included in the test run average provided that such
results are replaced with results from a test run meeting the criteria
above.

8.2 Catalytic Combustor and Wood Heater Aging. The catalyst-equipped
wood heater or a wood heater of any type shall be aged before the
certification test begins. The aging procedure shall be conducted and
documented by a testing laboratory accredited according to procedures in
Sec. 60.535 of 40 CFR part 60.
8.2.1 Catalyst-equipped Wood Heater. Operate the catalyst-equipped
wood heater using fuel meeting the specifications outlined in Sections
7.1.1 through 7.1.3, or cordwood with a moisture content between 15 and
25 percent on a wet basis. Operate the wood heater at a medium burn rate
(Category 2 or 3) with a new catalytic combustor in place and in
operation for at least 50 hours. Record and report hourly catalyst exit
temperature data (Section 8.6.2) and the hours of operation.
8.2.2 Non-Catalyst Wood Heater. Operate the wood heater using the
fuel described in Section 8.4.1 at a medium burn rate for at least 10
hours. Record and report the hours of operation.
8.3 Pretest Recordkeeping. Record the test fuel charge dimensions
and weights, and wood heater and catalyst descriptions as shown in the
example in Figure 28-1.
8.4 Wood Heater Installation. Assemble the wood heater appliance and
parts in conformance with the manufacturer's written installation
instructions. Place the wood heater centrally on the platform scale and
connect the wood heater to the flue described in Section 6.11. Clean the
flue with an appropriately sized, wire chimney brush before each
certification test.
8.5 Wood Heater Temperature Monitors.
8.5.1 For catalyst-equipped wood heaters, locate a temperature
monitor (optional) about 25 mm (1 in.) upstream of the catalyst at the
centroid of the catalyst face area, and locate a temperature monitor
(mandatory) that will indicate the catalyst exhaust temperature. This
temperature monitor is centrally located within 25 mm (1 in.) downstream
at the centroid of catalyst face area. Record these locations.
8.5.2 Locate wood heater surface temperature monitors at five
locations on the wood heater firebox exterior surface. Position the
temperature monitors centrally on the top surface, on two sidewall
surfaces, and on the bottom and back surfaces. Position the monitor
sensing tip on the firebox exterior surface inside of any heat shield,
air circulation walls, or other wall or shield separated from the
firebox exterior surface. Surface temperature locations for unusual
design shapes (e.g., spherical, etc.) shall be positioned so that there
are four surface temperature monitors in both the vertical and
horizontal planes passing at right angles through the centroid of the
firebox, not including the fuel loading door (total of five temperature
monitors).
8.6 Test Facility Conditions.
8.6.1 Locate the test facility temperature monitor on the horizontal
plane that includes the primary air intake opening for the wood heater.
Locate the temperature monitor 1 to 2 m (3 to 6 ft) from the front of
the wood heater in the 90[deg] sector in front of the wood heater.
8.6.2 Use an anemometer to measure the air velocity. Measure and
record the room air velocity before the pretest ignition period (Section
8.7) and once immediately following the test run completion.
8.6.3 Measure and record the test facility's ambient relative
humidity, barometric pressure, and temperature before and after each
test run.
8.6.4 Measure and record the flue draft or static pressure in the
flue at a location no greater than 0.3 m (1 ft) above the flue connector
at the wood heater exhaust during the test run at the recording
intervals (Section 8.8.2).
8.7 Wood Heater Firebox Volume.
8.7.1 Determine the firebox volume using the definitions for height,
width, and length in Section 3. Volume adjustments due to presence of
firebrick and other permanent fixtures may be necessary. Adjust width
and length dimensions to extend to the metal wall of the wood heater
above the firebrick or permanent obstruction if the firebrick or
obstruction extending the length of the side(s) or back wall extends
less than one-third of the usable firebox height. Use the width or
length dimensions inside the firebrick if the firebrick extends more
than one-third of the usable firebox height. If a log retainer or grate
is a permanent fixture and the manufacturer recommends that no fuel be
placed outside the retainer, the area outside of the retainer is
excluded from the firebox volume calculations.
8.7.2 In general, exclude the area above the ash lip if that area is
less than 10 percent of the usable firebox volume. Otherwise, take into
account consumer loading practices. For instance, if fuel is to be
loaded front-to-back, an ash lip may be considered usable firebox
volume.
8.7.3 Include areas adjacent to and above a baffle (up to two inches
above the fuel loading opening) if four inches or more horizontal space
exist between the edge of the baffle and a vertical obstruction (e.g.,
sidewalls or air channels).
8.8 Test Fuel Charge.
8.8.1 Prepare the test fuel pieces in accordance with the
specifications outlined in Sections 7.1 and 7.2. Determine the test fuel

[[Page 572]]

moisture content with a calibrated electrical resistance meter or other
equivalent performance meter. If necessary, convert fuel moisture
content values from dry basis (%Md) to wet basis
(%Mw) in Section 12.2 using Equation 28-1. Determine fuel
moisture for each fuel piece (not including spacers) by averaging at
least three moisture meter readings, one from each of three sides,
measured parallel to the wood grain. Average all the readings for all
the fuel pieces in the test fuel charge. If an electrical resistance
type meter is used, penetration of insulated electrodes shall be one-
fourth the thickness of the test fuel piece or 19 mm (0.75 in.),
whichever is greater. Measure the moisture content within a 4-hour
period prior to the test run. Determine the fuel temperature by
measuring the temperature of the room where the wood has been stored for
at least 24 hours prior to the moisture determination.
8.8.2 Attach the spacers to the test fuel pieces with uncoated,
ungalvanized nails or staples as illustrated in Figure 28-2. Attachment
of spacers to the top of the test fuel piece(s) on top of the test fuel
charge is optional.
8.8.3 To avoid stacking difficulties, or when a whole number of test
fuel pieces does not result, all piece lengths shall be adjusted
uniformly to remain within the specified loading density. The shape of
the test fuel crib shall be geometrically similar to the shape of the
firebox volume without resorting to special angular or round cuts on the
individual fuel pieces.
8.8.4 The test fuel loading density shall be 112 11.2 kg/m\3\ (7 0.7 lb/ft3) of
usable firebox volume on a wet basis.
8.9 Sampling Equipment. Prepare the sampling equipment as defined by
the selected method (i.e., either Method 5G or Method 5H). Collect one
particulate emission sample for each test run.
8.10 Secondary Air Adjustment Validation.
8.10.1 If design drawings do not show the introduction of secondary
air into a chamber outside the firebox (see ``secondary air supply''
under Section 3.0, Definitions), conduct a separate test of the wood
heater's secondary air supply. Operate the wood heater at a burn rate in
Category 1 (Section 8.1.1) with the secondary air supply operated
following the manufacturer's written instructions. Start the secondary
air validation test run as described in Section 8.8.1, except no
emission sampling is necessary and burn rate data shall be recorded at
5-minute intervals.
8.10.2 After the start of the test run, operate the wood heater with
the secondary air supply set as per the manufacturer's instructions, but
with no adjustments to this setting. After 25 percent of the test fuel
has been consumed, adjust the secondary air supply controls to another
setting, as per the manufacturer's instructions. Record the burn rate
data (5-minute intervals) for 20 minutes following the air supply
adjustment.
8.10.3 Adjust the air supply control(s) to the original position(s),
operate at this condition for at least 20 minutes, and repeat the air
supply adjustment procedure above. Repeat the procedure three times at
equal intervals over the entire burn period as defined in Section 8.8.
If the secondary air adjustment results in a burn rate change of more
than an average of 25 percent between the 20-minute periods before and
after the secondary adjustments, the secondary air supply shall be
considered a primary air supply, and no adjustment to this air supply is
allowed during the test run.
8.10.4 The example sequence below describes a typical secondary air
adjustment validation check. The first cycle begins after at least 25
percent of the test fuel charge has been consumed.

Cycle 1
Part 1, sec air adjusted to final position--20 min
Part 2, sec air adjusted to final position--20 min
Part 3, sec air adjusted to final position--20 min
Cycle 2
Part 1, sec air adjusted to final position--20 min
Part 2, sec air adjusted to final position--20 min
Part 3, sec air adjusted to final position--20 min
Cycle 3
Part 1, sec air adjusted to final position--20 min
Part 2, sec air adjusted to final position--20 min
Part 3, sec air adjusted to final position--20 min

Note that the cycles may overlap; that is, Part 3 of Cycle 1 may
coincide in part or in total with Part 1 of Cycle 2. The calculation of
the secondary air percent effect for this example is as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.425

[[Page 573]]

8.11 Pretest Ignition. Build a fire in the wood heater in accordance
with the manufacturer's written instructions.
8.11.1 Pretest Fuel Charge. Crumpled newspaper loaded with kindling
may be used to help ignite the pretest fuel. The pretest fuel, used to
sustain the fire, shall meet the same fuel requirements prescribed in
Section 7.1. The pretest fuel charge shall consist of whole 2x4's that
are no less than \1/3\ the length of the test fuel pieces. Pieces of 4x4
lumber in approximately the same weight ratio as for the test fuel
charge may be added to the pretest fuel charge.
8.11.2 Wood Heater Operation and Adjustments. Set the air inlet
supply controls at any position that will maintain combustion of the
pretest fuel load. At least one hour before the start of the test run,
set the air supply controls at the approximate positions necessary to
achieve the burn rate desired for the test run. Adjustment of the air
supply controls, fuel addition or subtractions, and coalbed raking shall
be kept to a minimum but are allowed up to 15 minutes prior to the start
of the test run. For the purposes of this method, coalbed raking is the
use of a metal tool (poker) to stir coals, break burning fuel into
smaller pieces, dislodge fuel pieces from positions of poor combustion,
and check for the condition of uniform charcoalization. Record all
adjustments made to the air supply controls, adjustments to and
additions or subtractions of fuel, and any other changes to wood heater
operations that occur during pretest ignition period. Record fuel weight
data and wood heater temperature measurements at 10-minute intervals
during the hour of the pretest ignition period preceding the start of
the test run. During the 15-minute period prior to the start of the test
run, the wood heater loading door shall not be open more than a total of
1 minute. Coalbed raking is the only adjustment allowed during this
period.

Note: One purpose of the pretest ignition period is to achieve
uniform charcoalization of the test fuel bed prior to loading the test
fuel charge. Uniform charcoalization is a general condition of the test
fuel bed evidenced by an absence of large pieces of burning wood in the
coal bed and the remaining fuel pieces being brittle enough to be broken
into smaller charcoal pieces with a metal poker. Manipulations to the
fuel bed prior to the start of the test run should be done to achieve
uniform charcoalization while maintaining the desired burn rate. In
addition, some wood heaters (e.g., high mass units) may require extended
pretest burn time and fuel additions to reach an initial average surface
temperature sufficient to meet the thermal equilibrium criteria in
Section 8.3.

8.11.3 The weight of pretest fuel remaining at the start of the test
run is determined as the difference between the weight of the wood
heater with the remaining pretest fuel and the tare weight of the
cleaned, dry wood heater with or without dry ash or sand added
consistent with the manufacturer's instructions and the owner's manual.
The tare weight of the wood heater must be determined with the wood
heater (and ash, if added) in a dry condition.
8.12 Test Run. Complete a test run in each burn rate category, as
follows:
8.12.1 Test Run Start.
8.12.1.1 When the kindling and pretest fuel have been consumed to
leave a fuel weight between 20 and 25 percent of the weight of the test
fuel charge, record the weight of the fuel remaining and start the test
run. Record and report any other criteria, in addition to those
specified in this section, used to determine the moment of the test run
start (e.g., firebox or catalyst temperature), whether such criteria are
specified by the wood heater manufacturer or the testing laboratory.
Record all wood heater individual surface temperatures, catalyst
temperatures, any initial sampling method measurement values, and begin
the particulate emission sampling. Within 1 minute following the start
of the test run, open the wood heater door, load the test fuel charge,
and record the test fuel charge weight. Recording of average, rather
than individual, surface temperatures is acceptable for tests conducted
in accordance with Sec. 60.533(o)(3)(i) of 40 CFR part 60.
8.12.1.2 Position the fuel charge so that the spacers are parallel
to the floor of the firebox, with the spacer edges abutting each other.
If loading difficulties result, some fuel pieces may be placed on edge.
If the usable firebox volume is between 0.043 and 0.085 m\3\ (1.5 and
3.0 ft\3\), alternate the piece sizes in vertical stacking layers to the
extent possible. For example, place 2 x 4's on the bottom layer in
direct contact with the coal bed and 4 x 4's on the next layer, etc.
(See Figure 28-3). Position the fuel pieces parallel to each other and
parallel to the longest wall of the firebox to the extent possible
within the specifications in Section 8.8.
8.12.1.3 Load the test fuel in appliances having unusual or
unconventional firebox design maintaining air space intervals between
the test fuel pieces and in conformance with the manufacturer's written
instructions. For any appliance that will not accommodate the loading
arrangement specified in the paragraph above, the test facility
personnel shall contact the Administrator for an alternative loading
arrangement.
8.12.1.4 The wood heater door may remain open and the air supply
controls adjusted up to five minutes after the start of the test run in
order to make adjustments to the test fuel charge and to ensure ignition
of the test fuel charge has occurred. Within the five minutes after the
start of the test run, close the wood heater door and adjust the air
supply controls to the position determined to produce

[[Page 574]]

the desired burn rate. No other adjustments to the air supply controls
or the test fuel charge are allowed (except as specified in Sections
8.12.3 and 8.12.4) after the first five minutes of the test run. Record
the length of time the wood heater door remains open, the adjustments to
the air supply controls, and any other operational adjustments.
8.12.2 Data Recording. Record on a data sheet similar to that shown
in Figure 28-4, at intervals no greater than 10 minutes, fuel weight
data, wood heater individual surface and catalyst temperature
measurements, other wood heater operational data (e.g., draft), test
facility temperature and sampling method data.
8.12.3 Test Fuel Charge Adjustment. The test fuel charge may be
adjusted (i.e., repositioned) once during a test run if more than 60
percent of the initial test fuel charge weight has been consumed and
more than 10 minutes have elapsed without a measurable (<0.05 kg (0.1
lb) or 1.0 percent, whichever is greater) weight change. The time used
to make this adjustment shall be less than 15 seconds.
8.12.4 Air Supply Adjustment. Secondary air supply controls may be
adjusted once during the test run following the manufacturer's written
instructions (see Section 8.10). No other air supply adjustments are
allowed during the test run. Recording of wood heater flue draft during
the test run is optional for tests conducted in accordance with Sec.
60.533(o)(3)(i) of 40 CFR part 60.
8.12.5 Auxiliary Wood Heater Equipment Operation. Heat exchange
blowers sold with the wood heater shall be operated during the test run
following the manufacturer's written instructions. If no manufacturer's
written instructions are available, operate the heat exchange blower in
the ``high'' position. (Automatically operated blowers shall be operated
as designed.) Shaker grates, by-pass controls, or other auxiliary
equipment may be adjusted only one time during the test run following
the manufacturer's written instructions.
Record all adjustments on a wood heater operational written record.

Note: If the wood heater is sold with a heat exchange blower as an
option, test the wood heater with the heat exchange blower operating as
described in Sections 8.1 through 8.12 and report the results. As an
alternative to repeating all test runs without the heat exchange blower
operating, one additional test run may be without the blower operating
as described in Section 8.12.5 at a burn rate in Category 2 (Section
8.1.1). If the emission rate resulting from this test run without the
blower operating is equal to or less than the emission rate plus 1.0 g/
hr (0.0022 lb/hr) for the test run in burn rate Category 2 with the
blower operating, the wood heater may be considered to have the same
average emission rate with or without the blower operating. Additional
test runs without the blower operating are unnecessary.

8.13 Test Run Completion. Continue emission sampling and wood heater
operation for 2 hours. The test run is completed when the remaining
weight of the test fuel charge is 0.00 kg (0.0 lb). End the test run
when the scale has indicated a test fuel charge weight of 0.00 kg (0.0
lb) or less for 30 seconds. At the end of the test run, stop the
particulate sampling, and record the final fuel weight, the run time,
and all final measurement values.
8.14 Wood Heater Thermal Equilibrium. The average of the wood heater
surface temperatures at the end of the test run shall agree with the
average surface temperature at the start of the test run to within 70
[deg]C (126 [deg]F).
8.15 Consecutive Test Runs. Test runs on a wood heater may be
conducted consecutively provided that a minimum one-hour interval occurs
between test runs.
8.16 Additional Test Runs. The testing laboratory may conduct more
than one test run in each of the burn rate categories specified in
Section 8.1.1. If more than one test run is conducted at a specified
burn rate, the results from at least two-thirds of the test runs in that
burn rate category shall be used in calculating the weighted average
emission rate (see Section 12.2). The measurement data and results of
all test runs shall be reported regardless of which values are used in
calculating the weighted average emission rate (see Note in Section
8.1).

9.0 Quality Control

Same as Section 9.0 of either Method 5G or Method 5H.

10.0 Calibration and Standardizations

Same as Section 10.0 of either Method 5G or Method 5H, with the
addition of the following:
10.1 Platform Scale. Perform a multi-point calibration (at least
five points spanning the operational range) of the platform scale before
its initial use. The scale manufacturer's calibration results are
sufficient for this purpose. Before each certification test, audit the
scale with the wood heater in place by weighing at least one calibration
weight (Class F) that corresponds to between 20 percent and 80 percent
of the expected test fuel charge weight. If the scale cannot reproduce
the value of the calibration weight within 0.05 kg (0.1 lb) or 1 percent
of the expected test fuel charge weight, whichever is greater,
recalibrate the scale before use with at least five calibration weights
spanning the operational range of the scale.
10.2 Balance (optional). Calibrate as described in Section 10.1.

[[Page 575]]

10.3 Temperature Monitor. Calibrate as in Method 2, Section 4.3,
before the first certification test and semiannually thereafter.
10.4 Moisture Meter. Calibrate as per the manufacturer's
instructions before each certification test.
10.5 Anemometer. Calibrate the anemometer as specified by the
manufacturer's instructions before the first certification test and
semiannually thereafter.
10.6 Barometer. Calibrate against a mercury barometer before the
first certification test and semiannually thereafter.
10.7 Draft Gauge. Calibrate as per the manufacturer's instructions;
a liquid manometer does not require calibration.
10.8 Humidity Gauge. Calibrate as per the manufacturer's
instructions before the first certification test and semiannually
thereafter.

11.0 Analytical Procedures

Same as Section 11.0 of either Method 5G or Method 5H.

12.0 Data Analysis and Calculations

Same as Section 12.0 of either Method 5G or Method 5H, with the
addition of the following:
12.1 Nomenclature.

BR=Dry wood burn rate, kg/hr (lb/hr)
Ei=Emission rate for test run, i, from Method 5G or 5H, g/hr
(lb/hr)
Ew=Weighted average emission rate, g/hr (lb/hr)
ki=Test run weighting factor=Pi+1 -
Pi-1
%Md=Fuel moisture content, dry basis, percent.
%Mw=Average moisture in test fuel charge, wet basis, percent.
n=Total number of test runs.
Pi=Probability for burn rate during test run, i, obtained
from Table 28-1. Use linear interpolation to determine probability
values for burn rates between those listed on the table.
Wwd=Total mass of wood burned during the test run, kg (lb).

12.2 Wet Basis Fuel Moisture Content.
[GRAPHIC] [TIFF OMITTED] TR17OC00.426

12.3 Weighted Average Emission Rate. Calculate the weighted average
emission rate (Ew) using Equation 28-1:
[GRAPHIC] [TIFF OMITTED] TR17OC00.427

Note: Po always equals 0, P(n+1) always equals
1, P1 corresponds to the probability of the lowest recorded
burn rate, P2 corresponds to the probability of the next
lowest burn rate, etc. An example calculation is in Section 12.3.1.

12.3.1 Example Calculation of Weighted Average Emission Rate.

------------------------------------------------------------------------
Burn rate Emissions
Burn rate category Test No. (Dry-kg/hr) (g/hr)
------------------------------------------------------------------------
1................................ 1 0.65 5.0
2\1\............................. 2 0.85 6.7
2................................ 3 0.90 4.7
2................................ 4 1.00 5.3
3................................ 5 1.45 3.8
4................................ 6 2.00 5.1
------------------------------------------------------------------------
\1\ As permitted in Section 6.6, this test run may be omitted from the
calculation of the weighted average emission rate because three runs
were conducted for this burn rate category.

----------------------------------------------------------------------------------------------------------------
Test No. Burn rate Pi Ei Ki
----------------------------------------------------------------------------------------------------------------
0........................................................... ........... 0.000 ........... ...........
1........................................................... 0.65 0.121 5.0 0.300
2........................................................... 0.90 0.300 4.7 0.259
3........................................................... 1.00 0.380 5.3 0.422
4........................................................... 1.45 0.722 3.8 0.532
5........................................................... 2.00 0.912 5.1 0.278
6........................................................... ........... 1.000 ........... ...........
----------------------------------------------------------------------------------------------------------------
K1=P2 - P0=0.300 - 0=0.300
K2=P3 - P1=0.381 - 0.121=0.259
K3=P4 - P2=0.722 - 0.300=0.422
K4=P5 - P3=0.912 - 0.380=0.532
K5=P6 - P4=1.000 - 0.722=0.278

Weighted Average Emission Rate, Ew, Calculation

[[Page 576]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.428

12.4 Average Wood Heater Surface Temperatures. Calculate the average
of the wood heater surface temperatures for the start of the test run
(Section 8.12.1) and for the test run completion (Section 8.13). If the
two average temperatures do not agree within 70 [deg]C (125 [deg]F),
report the test run results, but do not include the test run results in
the test average. Replace such test run results with results from
another test run in the same burn rate category.
12.5 Burn Rate. Calculate the burn rate (BR) using Equation 28-3:
[GRAPHIC] [TIFF OMITTED] TR17OC00.429

12.6 Reporting Criteria. Submit both raw and reduced test data for
wood heater tests.
12.6.1 Suggested Test Report Format.
12.6.1.1 Introduction.
12.6.1.1.1 Purpose of test-certification, audit, efficiency,
research and development.
12.6.1.1.2 Wood heater identification-manufacturer, model number,
catalytic/noncatalytic, options.
12.6.1.1.3 Laboratory-name, location (altitude), participants.
12.6.1.1.4 Test information-date wood heater received, date of
tests, sampling methods used, number of test runs.
12.6.1.2 Summary and Discussion of Results
12.6.1.2.1 Table of results (in order of increasing burn rate)-test
run number, burn rate, particulate emission rate, efficiency (if
determined), averages (indicate which test runs are used).
12.6.1.2.2 Summary of other data-test facility conditions, surface
temperature averages, catalyst temperature averages, pretest fuel
weights, test fuel charge weights, run times.
12.6.1.2.3 Discussion-Burn rate categories achieved, test run result
selection, specific test run problems and solutions.
12.6.1.3 Process Description.
12.6.1.3.1 Wood heater dimensions-volume, height, width, lengths (or
other linear dimensions), weight, volume adjustments.
12.6.1.3.2 Firebox configuration-air supply locations and operation,
air supply introduction location, refractory location and dimensions,
catalyst location, baffle and by-pass location and operation (include
line drawings or photographs).
12.6.1.3.3 Process operation during test-air supply settings and
adjustments, fuel bed adjustments, draft.
12.6.1.3.4 Test fuel-test fuel properties (moisture and
temperature), test fuel crib description (include line drawing or
photograph), test fuel loading density.
12.6.1.4 Sampling Locations.
12.6.1.4.1 Describe sampling location relative to wood heater.
Include drawing or photograph.
12.6.1.5 Sampling and Analytical Procedures
12.6.1.5.1 Sampling methods-brief reference to operational and
sampling procedures and optional and alternative procedures used.
12.6.1.5.2 Analytical methods-brief description of sample recovery
and analysis procedures.
12.6.1.6 Quality Control and Assurance Procedures and Results
12.6.1.6.1 Calibration procedures and results-certification
procedures, sampling and analysis procedures.
12.6.1.6.2 Test method quality control procedures-leak-checks,
volume meter checks, stratification (velocity) checks, proportionality
results.
12.6.1.7 Appendices
12.6.1.7.1 Results and Example Calculations. Complete summary tables
and accompanying examples of all calculations.
12.6.1.7.2 Raw Data. Copies of all uncorrected data sheets for
sampling measurements, temperature records and sample recovery data.
Copies of all pretest burn rate and wood heater temperature data.

[[Page 577]]

12.6.1.7.3 Sampling and Analytical Procedures. Detailed description
of procedures followed by laboratory personnel in conducting the
certification test, emphasizing particular parts of the procedures
differing from the methods (e.g., approved alternatives).
12.6.1.7.4 Calibration Results. Summary of all calibrations, checks,
and audits pertinent to certification test results with dates.
12.6.1.7.5 Participants. Test personnel, manufacturer
representatives, and regulatory observers.
12.6.1.7.6 Sampling and Operation Records. Copies of uncorrected
records of activities not included on raw data sheets (e.g., wood heater
door open times and durations).
12.6.1.7.7 Additional Information. Wood heater manufacturer's
written instructions for operation during the certification test.
12.6.2.1 Wood Heater Identification. Report wood heater
identification information. An example data form is shown in Figure 28-
4.
12.6.2.2 Test Facility Information. Report test facility
temperature, air velocity, and humidity information. An example data
form is shown on Figure 28-4.
12.6.2.3 Test Equipment Calibration and Audit Information. Report
calibration and audit results for the platform scale, test fuel balance,
test fuel moisture meter, and sampling equipment including volume
metering systems and gaseous analyzers.
12.6.2.4 Pretest Procedure Description. Report all pretest
procedures including pretest fuel weight, burn rates, wood heater
temperatures, and air supply settings. An example data form is shown on
Figure 28-4.
12.6.2.5 Particulate Emission Data. Report a summary of test results
for all test runs and the weighted average emission rate. Submit copies
of all data sheets and other records collected during the testing.
Submit examples of all calculations.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

16.1 Pellet Burning Heaters. Certification testing requirements and
procedures for pellet burning wood heaters are identical to those for
other wood heaters, with the following exceptions:
16.1.1 Test Fuel Properties. The test fuel shall be all wood pellets
with a moisture content no greater than 20 percent on a wet basis (25
percent on a dry basis). Determine the wood moisture content with either
ASTM D 2016-74 or 83, (Method A), ASTM D 4444-92, or ASTM D 4442-84 or
92 (all noted ASTM standards are incorporated by reference--see Sec.
60.17).
16.1.2 Test Fuel Charge Specifications. The test fuel charge size
shall be as per the manufacturer's written instructions for maintaining
the desired burn rate.
16.1.3 Wood Heater Firebox Volume. The firebox volume need not be
measured or determined for establishing the test fuel charge size. The
firebox dimensions and other heater specifications needed to identify
the heater for certification purposes shall be reported.
16.1.4 Heater Installation. Arrange the heater with the fuel supply
hopper on the platform scale as described in Section 8.6.1.
16.1.5 Pretest Ignition. Start a fire in the heater as directed by
the manufacturer's written instructions, and adjust the heater controls
to achieve the desired burn rate. Operate the heater at the desired burn
rate for at least 1 hour before the start of the test run.
16.1.6 Test Run. Complete a test run in each burn rate category as
follows:
16.1.6.1 Test Run Start. When the wood heater has operated for at
least 1 hour at the desired burn rate, add fuel to the supply hopper as
necessary to complete the test run, record the weight of the fuel in the
supply hopper (the wood heater weight), and start the test run. Add no
additional fuel to the hopper during the test run.
Record all the wood heater surface temperatures, the initial
sampling method measurement values, the time at the start of the test,
and begin the emission sampling. Make no adjustments to the wood heater
air supply or wood supply rate during the test run.
16.1.6.2 Data Recording. Record the fuel (wood heater) weight data,
wood heater temperature and operational data, and emission sampling data
as described in Section 8.12.2.
16.1.6.3 Test Run Completion. Continue emission sampling and wood
heater operation for 2 hours. At the end of the test run, stop the
particulate sampling, and record the final fuel weight, the run time,
and all final measurement values, including all wood heater individual
surface temperatures.
16.1.7 Calculations. Determine the burn rate using the difference
between the initial and final fuel (wood heater) weights and the
procedures described in Section 12.4. Complete the other calculations as
described in Section 12.0.

17.0 References

Same as Method 5G, with the addition of the following:

1. Radian Corporation. OMNI Environmental Services, Inc., Cumulative
Probability for a Given Burn Rate Based on Data Generated in the CONEG
and BPA Studies. Package of materials submitted to the Fifth Session of
the Regulatory Negotiation Committee, July 16-17, 1986.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 578]]

Table 28-1--Burn Rate Weighted Probabilities for Calculating Weighted Average Emission Rates
----------------------------------------------------------------------------------------------------------------
Cumulative Cumulative Cumulative
Burn rate (kg/hr-dry) probability Burn rate (kg/ probability Burn rate (kg/ probability
(P) hr-dry) (P) hr-dry) (P)
----------------------------------------------------------------------------------------------------------------
0.00............................ 0.000 1.70 0.840 3.40 0.989
0.05............................ 0.002 1.75 0.857 3.45 0.989
0.10............................ 0.007 1.80 0.875 3.50 0.990
0.15............................ 0.012 1.85 0.882 3.55 0.991
0.20............................ 0.016 1.90 0.895 3.60 0.991
0.25............................ 0.021 1.95 0.906 3.65 0.992
0.30............................ 0.028 2.00 0.912 3.70 0.992
0.35............................ 0.033 2.05 0.920 3.75 0.992
0.40............................ 0.041 2.10 0.925 3.80 0.993
0.45............................ 0.054 2.15 0.932 3.85 0.994
0.50............................ 0.065 2.20 0.936 3.90 0.994
0.55............................ 0.086 2.25 0.940 3.95 0.994
0.60............................ 0.100 2.30 0.945 4.00 0.994
0.65............................ 0.121 2.35 0.951 4.05 0.995
0.70............................ 0.150 2.40 0.956 4.10 0.995
0.75............................ 0.185 2.45 0.959 4.15 0.995
0.80............................ 0.220 2.50 0.964 4.20 0.995
0.85............................ 0.254 2.55 0.968 4.25 0.995
0.90............................ 0.300 2.60 0.972 4.30 0.996
0.95............................ 0.328 2.65 0.975 4.35 0.996
1.00............................ 0.380 2.70 0.977 4.40 0.996
1.05............................ 0.407 2.75 0.979 4.45 0.996
1.10............................ 0.460 2.80 0.980 4.50 0.996
1.15............................ 0.490 2.85 0.981 4.55 0.996
1.20............................ 0.550 2.90 0.982 4.60 0.996
1.25............................ 0.572 2.95 0.984 4.65 0.996
1.30............................ 0.620 3.00 0.984 4.70 0.996
1.35............................ 0.654 3.05 0.985 4.75 0.997
1.40............................ 0.695 3.10 0.986 4.80 0.997
1.45............................ 0.722 3.15 0.987 4.85 0.997
1.50............................ 0.750 3.20 0.987 4.90 0.997
1.55............................ 0.779 3.25 0.988 4.95 0.997
1.60............................ 0.800 3.30 0.988 =5. 1.000
00
1.65............................ 0.825 3.35 0.989 .............. ..............
----------------------------------------------------------------------------------------------------------------

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[GRAPHIC] [TIFF OMITTED] TR17OC00.430

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[GRAPHIC] [TIFF OMITTED] TR17OC00.431

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[GRAPHIC] [TIFF OMITTED] TR17OC00.432

Method 28A--Measurement of Air- to-Fuel Ratio and Mimimum Achievable
Burn Rates for Wood-Fired Appliances

Note: This method does not include all or 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 at
least the following additional test methods: Method 3, Method 3A, Method
5H, Method 6C, and Method 28.

1.0 Scope and Application

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

[[Page 582]]

1.2 Applicability. This method is applicable for the measurement of
air-to-fuel ratios and minimum achievable burn rates, for determining
whether a wood-fired appliance is an affected facility, as specified in
40 CFR 60.530.
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 a location in the stack of a
wood-fired appliance while the appliance is operating at a prescribed
set of conditions. The gas sample is analyzed for carbon dioxide
(CO2), oxygen (O2), and carbon monoxide (CO).
These stack gas components are measured for determining the dry
molecular weight of the exhaust gas. Total moles of exhaust gas are
determined stoichiometrically. Air-to-fuel ratio is determined by
relating the mass of dry combustion air to the mass of dry fuel
consumed.

3.0 Definitions

Same as Method 28, Section 3.0, with the addition of the following:
3.1 Air-to-fuel ratio means the ratio of the mass of dry combustion
air introduced into the firebox to the mass of dry fuel consumed (grams
of dry air per gram of dry wood burned).

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

6.1 Test Facility. Insulated Solid Pack Chimney, Platform Scale and
Monitor, Test Facility Temperature Monitor, Balance, Moisture Meter,
Anemometer, Barometer, Draft Gauge, Humidity Gauge, Wood Heater Flue,
and Test Facility. Same as Method 28, Sections 6.1, 6.2, and 6.4 to
6.12, respectively.
6.2 Sampling System. Probe, Condenser, Valve, Pump, Rate Meter,
Flexible Bag, Pressure Gauge, and Vacuum Gauge. Same as Method 3,
Sections 6.2.1 to 6.2.8, respectively. Alternatively, the sampling
system described in Method 5H, Section 6.1 may be used.
6.3 Exhaust Gas Analysis. Use one or both of the following:
6.3.1 Orsat Analyzer. Same as Method 3, Section 6.1.3
6.3.2 Instrumental Analyzers. Same as Method 5H, Sections 6.1.3.4
and 6.1.3.5, for CO2 and CO analyzers, except use a CO
analyzer with a range of 0 to 5 percent and use a CO2
analyzer with a range of 0 to 5 percent. Use an O2 analyzer
capable of providing a measure of O2 in the range of 0 to 25
percent by volume at least once every 10 minutes.

7.0 Reagents and Standards

7.1 Test Fuel and Test Fuel Spacers. Same as Method 28, Sections 7.1
and 7.2, respectively.
7.2 Cylinder Gases. For each of the three analyzers, use the same
concentration as specified in Sections 7.2.1, 7.2.2, and 7.2.3 of Method
6C.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Wood Heater Air Supply Adjustments.
8.1.1 This section describes how dampers are to be set or adjusted
and air inlet ports closed or sealed during Method 28A tests. The
specifications in this section are intended to ensure that affected
facility determinations are made on the facility configurations that
could reasonably be expected to be employed by the user. They are also
intended to prevent circumvention of the standard through the addition
of an air port that would often be blocked off in actual use. These
specifications are based on the assumption that consumers will remove
such items as dampers or other closure mechanism stops if this can be
done readily with household tools; that consumers will block air inlet
passages not visible during normal operation of the appliance using
aluminum tape or parts generally available at retail stores; and that
consumers will cap off any threaded or flanged air inlets. They also
assume that air leakage around glass doors, sheet metal joints or
through inlet grilles visible during normal operation of the appliance
would not be further blocked or taped off by a consumer.
8.1.2 It is not the intention of this section to cause an appliance
that is clearly designed, intended, and, in most normal installations,
used as a fireplace to be converted into a wood heater for purposes of
applicability testing. Such a fireplace would be identifiable by such
features as large or multiple glass doors or panels that are not
gasketed, relatively unrestricted air inlets intended, in large part, to
limit smoking and fogging of glass surfaces, and other aesthetic
features not normally included in wood heaters.
8.1.3 Adjustable Air Supply Mechanisms. Any commercially available
flue damper, other adjustment mechanism or other air

[[Page 583]]

inlet port that is designed, intended or otherwise reasonably expected
to be adjusted or closed by consumers, installers, or dealers and which
could restrict air into the firebox shall be set so as to achieve
minimum air into the firebox (i.e., closed off or set in the most closed
position).
8.1.3.1 Flue dampers, mechanisms and air inlet ports which could
reasonably be expected to be adjusted or closed would include:
8.1.3.1.1 All internal or externally adjustable mechanisms
(including adjustments that affect the tightness of door fittings) that
are accessible either before and/or after installation.
8.1.3.1.2 All mechanisms, other inlet ports, or inlet port stops
that are identified in the owner's manual or in any dealer literature as
being adjustable or alterable. For example, an inlet port that could be
used to provide access to an outside air duct but which is identified as
being closable through use of additional materials whether or not they
are supplied with the facility.
8.1.3.1.3 Any combustion air inlet port or commercially available
flue damper or mechanism stop, which would readily lend itself to
closure by consumers who are handy with household tools by the removal
of parts or the addition of parts generally available at retail stores
(e.g., addition of a pipe cap or plug, addition of a small metal plate
to an inlet hole on a nondecorative sheet metal surface, or removal of
riveted or screwed damper stops).
8.1.3.1.4 Any flue damper, other adjustment mechanisms or other air
inlet ports that are found and documented in several (e.g., a number
sufficient to reasonably conclude that the practice is not unique or
uncommon) actual installations as having been adjusted to a more closed
position, or closed by consumers, installers, or dealers.
8.1.4 Air Supply Adjustments During Test. The test shall be
performed with all air inlets identified under this section in the
closed or most closed position or in the configuration which otherwise
achieves the lowest air inlet (i.e., greatest blockage).

Note: For the purposes of this section, air flow shall not be
minimized beyond the point necessary to maintain combustion or beyond
the point that forces smoke into the room.

8.1.5 Notwithstanding Section 8.1.1, any flue damper, adjustment
mechanism, or air inlet port (whether or not equipped with flue dampers
or adjusting mechanisms) that is visible during normal operation of the
appliance and which could not reasonably be closed further or blocked
except through means that would significantly degrade the aesthetics of
the facility (e.g., through use of duct tape) will not be closed further
or blocked.
8.2 Sampling System.
8.2.1 Sampling Location. Same as Method 5H, Section 8.1.2.
8.2.2 Sampling System Set Up. Set up the sampling equipment as
described in Method 3, Section 8.1.
8.3 Wood Heater Installation, Test Facility Conditions, Wood Heater
Firebox Volume, and Test Fuel Charge. Same as Method 28, Sections 8.4
and 8.6 to 8.8, respectively.
8.4 Pretest Ignition. Same as Method 28, Section 8.11. Set the wood
heater air supply settings to achieve a burn rate in Category 1 or the
lowest achievable burn rate (see Section 8.1).
8.5 Test Run. Same as Method 28, Section 8.12. Begin sample
collection at the start of the test run as defined in Method 28, Section
8.12.1.
8.5.1 Gas Analysis.
8.5.1.1 If Method 3 is used, collect a minimum of two bag samples
simultaneously at a constant sampling rate for the duration of the test
run. A minimum sample volume of 30 liters (1.1 ft\3\) per bag is
recommended.
8.5.1.2 If instrumental gas concentration measurement procedures are
used, conduct the gas measurement system performance tests, analyzer
calibration, and analyzer calibration error check outlined in Method 6C,
Sections 8.2.3, 8.2.4, 8.5, and 10.0, respectively. Sample at a constant
rate for the duration of the test run.
8.5.2 Data Recording. Record wood heater operational data, test
facility temperature, sample train flow rate, and fuel weight data at
intervals of no greater than 10 minutes.
8.5.3 Test Run Completion. Same as Method 28, Section 8.13.

9.0 Quality Control

9.1 Data Validation. The following quality control procedure is
suggested to provide a check on the quality of the data.
9.1.1 Calculate a fuel factor, Fo, using Equation 28A-1
in Section 12.2.
9.1.2 If CO is present in quantities measurable by this method,
adjust the O2 and CO2 values before performing the
calculation for Fo as shown in Section 12.3 and 12.4.
9.1.3 Compare the calculated Fo factor with the expected
Fo range for wood (1.000-1.120). Calculated Fo
values beyond this acceptable range should be investigated before
accepting the test results. For example, the strength of the solutions
in the gas analyzer and the analyzing technique should be checked by
sampling and analyzing a known concentration, such as air. If no
detectable or correctable measurement error can be identified, the test
should be repeated. Alternatively, determine a range of air-to-fuel
ratio results that could include the correct value by using an
Fo value of 1.05 and calculating a potential range of
CO2 and O2 values. Acceptance of such results will
be based on whether the calculated range includes the

[[Page 584]]

exemption limit and the judgment of the Administrator.
9.2 Method 3 Analyses. Compare the results of the analyses of the
two bag samples. If all the gas components (O2, CO, and
CO2) values for the two analyses agree within 0.5 percent
(e.g., 6.0 percent O2 for bag 1 and 6.5 percent O2
for bag 2, agree within 0.5 percent), the results of the bag analyses
may be averaged for the calculations in Section 12. If the analysis
results do not agree within 0.5 percent for each component, calculate
the air-to-fuel ratio using both sets of analyses and report the
results.

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedures

11.1 Method 3 Integrated Bag Samples. Within 4 hours after the
sample collection, analyze each bag sample for percent CO2,
O2, and CO using an Orsat analyzer as described in Method 3,
Section 11.0.
11.2 Instrumental Analyzers. Average the percent CO2, CO,
and O2 values for the test run.

12.0 Data Analyses and Calculations

Carry out calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figure after the
final calculation. Other forms of the equations may be used as long as
they give equivalent results.
12.1 Nomenclature.

Md=Dry molecular weight, g/g-mole (lb/lb-mole).
NT=Total gram-moles of dry exhaust gas per kg of wood burned
(lb-moles/lb).
%CO2=Percent CO2 by volume (dry basis).
%CO=Percent CO by volume (dry basis).
%N2=Percent N2 by volume (dry basis).
%O2=Percent O2 by volume (dry basis).
YHC=Assumed mole fraction of HC (dry as
CH4)=0.0088 for catalytic wood heaters;=0.0132 for
noncatalytic wood heaters.=0.0080 for pellet-fired wood heaters.
YCO=Measured mole fraction of CO (e.g., 1 percent CO=.01 mole
fraction), g/g-mole (lb/lb-mole).
YCO2=Measured mole fraction of COCO2 (e.g., 10
percent CO2=.10 mole fraction), g/g-mole (lb/lb-mole).
0.280=Molecular weight of N2 or CO, divided by 100.
0.320=Molecular weight of O2 divided by 100.
0.440=Molecular weight of CO2 divided by 100.
20.9=Percent O2 by volume in ambient air.
42.5=Gram-moles of carbon in 1 kg of dry wood assuming 51 percent carbon
by weight dry basis (.0425 lb/lb-mole).
510=Grams of carbon in exhaust gas per kg of wood burned.
1,000=Grams in 1 kg.

12.2 Fuel Factor. Use Equation 28A-1 to calculate the fuel factor.
[GRAPHIC] [TIFF OMITTED] TR17OC00.433

12. 3 Adjusted %CO2. Use Equation 28A-2 to adjust
CO2 values if measurable CO is present.
[GRAPHIC] [TIFF OMITTED] TR17OC00.434

12.4 Adjusted %O2. Use Equation 28A-3 to adjust
O2 value if measurable CO is present.
[GRAPHIC] [TIFF OMITTED] TR17OC00.435

12.5 Dry Molecular Weight. Use Equation 28A-4 to calculate the dry
molecular weight of the stack gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.436

Note: The above equation does not consider argon in air (about 0.9
percent, molecular weight of 39.9). A negative error of about 0.4
percent is introduced. Argon may

[[Page 585]]

be included in the analysis using procedures subject to approval of the
Administrator.

12.6 Dry Moles of Exhaust Gas. Use Equation 28A-5 to calculate the
total moles of dry exhaust gas produced per kilogram of dry wood burned.
[GRAPHIC] [TIFF OMITTED] TR17OC00.437

12.7 Air-to-Fuel Ratio. Use Equation 28A-6 to calculate the air-to-
fuel ratio on a dry mass basis.
[GRAPHIC] [TIFF OMITTED] TR17OC00.438

12.8 Burn Rate. Calculate the fuel burn rate as in Method 28,
Section 12.4.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as Section 16.0 of Method 3 and Section 17 of Method 5G.

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

Method 29--Determination of Metals Emissions From Stationary Sources

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Antimony (Sb)........................................... 7440-36-0
Arsenic (As)............................................ 7440-38-2
Barium (Ba)............................................. 7440-39-3
Beryllium (Be).......................................... 7440-41-7
Cadmium (Cd)............................................ 7440-43-9
Chromium (Cr)........................................... 7440-47-3
Cobalt (Co)............................................. 7440-48-4
Copper (Cu)............................................. 7440-50-8
Lead (Pb)............................................... 7439-92-1
Manganese (Mn).......................................... 7439-96-5
Mercury (Hg)............................................ 7439-97-6
Nickel (Ni)............................................. 7440-02-0
Phosphorus (P).......................................... 7723-14-0
Selenium (Se)........................................... 7782-49-2
Silver (Ag)............................................. 7440-22-4
Thallium (Tl)........................................... 7440-28-0
Zinc (Zn)............................................... 7440-66-6
------------------------------------------------------------------------

1.2 Applicability. This method is applicable to the determination of
metals emissions from stationary sources. This method may be used to
determine particulate emissions in addition to the metals emissions if
the prescribed procedures and precautions are followed.
1.2.1 Hg emissions can be measured, alternatively, using EPA Method
101A of Appendix B, 40 CFR Part 61. Method 101-A measures only Hg but it
can be of special interest to sources which need to measure both Hg and
Mn emissions.

2.0 Summary of Method

2.1 Principle. A stack sample is withdrawn isokinetically from the
source, particulate emissions are collected in the probe and on a heated
filter, and gaseous emissions are then collected in an aqueous acidic
solution of hydrogen peroxide (analyzed for all metals including Hg) and
an aqueous acidic solution of potassium permanganate (analyzed only for
Hg). The recovered samples are digested, and appropriate fractions are
analyzed for Hg by cold vapor atomic absorption spectroscopy (CVAAS) and
for Sb, As, Ba, Be, Cd, Cr, Co, Cu, Pb, Mn, Ni, P, Se, Ag, Tl, and Zn by
inductively coupled argon plasma emission spectroscopy (ICAP) or atomic
absorption spectroscopy (AAS). Graphite furnace atomic absorption
spectroscopy (GFAAS) is used for analysis of Sb, As, Cd, Co, Pb, Se, and
Tl if these elements require greater analytical sensitivity than can be
obtained by ICAP. If one so chooses, AAS may be used for analysis of all
listed metals if the resulting in-stack method detection limits meet the
goal of the testing program. Similarly, inductively coupled plasma-mass
spectroscopy (ICP-MS) may be used for analysis of Sb, As, Ba, Be, Cd,
Cr, Co, Cu, Pb, Mn, Ni, Ag, Tl and Zn.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Iron (Fe) can be a spectral interference during the analysis of
As, Cr, and Cd by ICAP. Aluminum (Al) can be a spectral interference
during the analysis of As and Pb by ICAP. Generally, these interferences
can be reduced by diluting the analytical sample, but such dilution
raises the in-stack detection limits. Background and overlap corrections
may be used to adjust for spectral interferences. Refer to Method 6010
of Reference 2 in Section 16.0 or the other analytical methods used for
details on potential interferences to this method. For all GFAAS
analyses, use matrix modifiers to limit interferences, and matrix match
all standards.

[[Page 586]]

5.0 Safety

5.1 Disclaimer. This method may involve hazardous materials,
operations, and equipment. This test method may not address all of the
safety problems associated with its use. It is the responsibility of the
user of this test method to establish appropriate safety and health
practices and to determine the applicability of regulatory limitations
prior to performing this test method.
5.2 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 at least 15 minutes. Remove clothing under
shower and decontaminate. Treat residual chemical burn as thermal burn.
5.2.1 Nitric Acid (HNO3). Highly corrosive to eyes, skin,
nose, and lungs. Vapors cause bronchitis, pneumonia, or edema of lungs.
Reaction to inhalation may be delayed as long as 30 hours and still be
fatal. Provide ventilation to limit exposure. Strong oxidizer. Hazardous
reaction may occur with organic materials such as solvents.
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/m\3\ for 8 hours will cause lung damage or, in higher
concentrations, death. Provide ventilation to limit inhalation. Reacts
violently with metals and organics.
5.2.3 Hydrochloric Acid (HC1). Highly corrosive liquid with toxic
vapors. Vapors are highly irritating to eyes, skin, nose, and lungs,
causing severe damage. May cause bronchitis, pneumonia, or edema of
lungs. Exposure to concentrations of 0.13 to 0.2 percent can be lethal
to humans in a few minutes. Provide ventilation to limit exposure.
Reacts with metals, producing hydrogen gas.
5.2.4 Hydrofluoric Acid (HF). Highly corrosive to eyes, skin, nose,
throat, and lungs. Reaction to exposure may be delayed by 24 hours or
more. Provide ventilation to limit exposure.
5.2.5 Hydrogen Peroxide (H2O2). Irritating to
eyes, skin, nose, and lungs. 30% H2O2 is a strong
oxidizing agent. Avoid contact with skin, eyes, and combustible
material. Wear gloves when handling.
5.2.6 Potassium Permanganate (KMnO4). Caustic, strong
oxidizer. Avoid bodily contact with.
5.2.7 Potassium Persulfate. Strong oxidizer. Avoid bodily contact
with. Keep containers well closed and in a cool place.
5.3 Reaction Pressure. Due to the potential reaction of the
potassium permanganate with the acid, there could be pressure buildup in
the acidic KMnO4 absorbing solution storage bottle. Therefore
these bottles shall not be fully filled and shall be vented to relieve
excess pressure and prevent explosion potentials. Venting is required,
but not in a manner that will allow contamination of the solution. A No.
70-72 hole drilled in the container cap and Teflon liner has been used.

6.0 Equipment and Supplies

6.1 Sampling. A schematic of the sampling train is shown in Figure
29-1. It has general similarities to the Method 5 train.
6.1.1 Probe Nozzle (Probe Tip) and Borosilicate or Quartz Glass
Probe Liner. Same as Method 5, Sections 6.1.1.1 and 6.1.1.2, except that
glass nozzles are required unless alternate tips are constructed of
materials that are free from contamination and will not interfere with
the sample. If a probe tip other than glass is used, no correction to
the sample test results to compensate for the nozzle's effect on the
sample is allowed. Probe fittings of plastic such as Teflon,
polypropylene, etc. are recommended instead of metal fittings to prevent
contamination. If one chooses to do so, a single glass piece consisting
of a combined probe tip and probe liner may be used.
6.1.2 Pitot Tube and Differential Pressure Gauge. Same as Method 2,
Sections 6.1 and 6.2, respectively.
6.1.3 Filter Holder. Glass, same as Method 5, Section 6.1.1.5,
except use a Teflon filter support or other non-metallic, non-
contaminating support in place of the glass frit.
6.1.4 Filter Heating System. Same as Method 5, Section 6.1.1.6.
6.1.5 Condenser. Use the following system for condensing and
collecting gaseous metals and determining the moisture content of the
stack gas. The condensing system shall consist of four to seven
impingers connected in series with leak-free ground glass fittings or
other leak-free, non-contaminating fittings. Use the first impinger as a
moisture trap. The second impinger (which is the first HNO3/
H2O2 impinger) shall be identical to the first
impinger in Method 5. The third impinger (which is the second
HNO3/H2O2 impinger) shall be a
Greenburg Smith impinger with the standard tip as described for the
second impinger in Method 5, Section 6.1.1.8. The fourth (empty)
impinger and the fifth and sixth (both acidified KMnO4)
impingers are the same as the first impinger in Method 5. Place a
temperature sensor capable of measuring to within 1 [deg]C (2 [deg]F) at
the outlet of the last impinger. If no Hg analysis is planned, then the
fourth, fifth, and sixth impingers are not used.
6.1.6 Metering System, Barometer, and Gas Density Determination
Equipment. Same as Method 5, Sections 6.1.1.9, 6.1.2, and 6.1.3,
respectively.
6.1.7 Teflon Tape. For capping openings and sealing connections, if
necessary, on the sampling train.

[[Page 587]]

6.2 Sample Recovery. Same as Method 5, Sections 6.2.1 through 6.2.8
(Probe-Liner and Probe-Nozzle Brushes or Swabs, Wash Bottles, Sample
Storage Containers, Petri Dishes, Glass Graduated Cylinder, Plastic
Storage Containers, Funnel and Rubber Policeman, and Glass Funnel),
respectively, with the following exceptions and additions:
6.2.1 Non-metallic Probe-Liner and Probe-Nozzle Brushes or Swabs.
Use non-metallic probe-liner and probe-nozzle brushes or swabs for
quantitative recovery of materials collected in the front-half of the
sampling train.
6.2.2 Sample Storage Containers. Use glass bottles (see Section 8.1
of this Method) with Teflon-lined caps that are non-reactive to the
oxidizing solutions, with capacities of 1000- and 500-ml, for storage of
acidified KMnO4--containing samples and blanks. Glass or
polyethylene bottles may be used for other sample types.
6.2.3 Graduated Cylinder. Glass or equivalent.
6.2.4 Funnel. Glass or equivalent.
6.2.5 Labels. For identifying samples.
6.2.6 Polypropylene Tweezers and/or Plastic Gloves. For recovery of
the filter from the sampling train filter holder.
6.3 Sample Preparation and Analysis.
6.3.1 Volumetric Flasks, 100-ml, 250-ml, and 1000-ml. For
preparation of standards and sample dilutions.
6.3.2 Graduated Cylinders. For preparation of reagents.
6.3.3 Parr Bombs or Microwave Pressure Relief Vessels with Capping
Station (CEM Corporation model or equivalent). For sample digestion.
6.3.4 Beakers and Watch Glasses. 250-ml beakers, with watch glass
covers, for sample digestion.
6.3.5 Ring Stands and Clamps. For securing equipment such as
filtration apparatus.
6.3.6 Filter Funnels. For holding filter paper.
6.3.7 Disposable Pasteur Pipets and Bulbs.
6.3.8 Volumetric Pipets.
6.3.9 Analytical Balance. Accurate to within 0.1 mg.
6.3.10 Microwave or Conventional Oven. For heating samples at fixed
power levels or temperatures, respectively.
6.3.11 Hot Plates.
6.3.12 Atomic Absorption Spectrometer (AAS). Equipped with a
background corrector.
6.3.12.1 Graphite Furnace Attachment. With Sb, As, Cd, Co, Pb, Se,
and Tl hollow cathode lamps (HCLs) or electrodeless discharge lamps
(EDLs). Same as Reference 2 in Section 16.0. Methods 7041 (Sb), 7060
(As), 7131 (Cd), 7201 (Co), 7421 (Pb), 7740 (Se), and 7841 (Tl).
6.3.12.2 Cold Vapor Mercury Attachment. With a mercury HCL or EDL,
an air recirculation pump, a quartz cell, an aerator apparatus, and a
heat lamp or desiccator tube. The heat lamp shall be capable of raising
the temperature at the quartz cell by 10 [deg]C above ambient, so that
no condensation forms on the wall of the quartz cell. Same as Method
7470 in Reference 2 in Section 16.0. See Note 2: Section 11.1.3 for
other acceptable approaches for analysis of Hg in which analytical
detection limits of 0.002 ng/ml were obtained.
6.3.13 Inductively Coupled Argon Plasma Spectrometer. With either a
direct or sequential reader and an alumina torch. Same as EPA Method
6010 in Reference 2 in Section 16.0.
6.3.14 Inductively Coupled Plasma-Mass Spectrometer.
Same as EPA Method 6020 in Reference 2 in Section 16.0.

7.0 Reagents and Standards

7.1 Unless otherwise indicated, it is intended that all reagents
conform to the specifications established by the Committee on Analytical
Reagents of the American Chemical Society, where such specifications are
available. Otherwise, use the best available grade.
7.2 Sampling Reagents.
7.2.1 Sample Filters. Without organic binders. The filters shall
contain less than 1.3 [micro]g/in.\2\ of each of the metals to be
measured. Analytical results provided by filter manufacturers stating
metals content of the filters are acceptable. However, if no such
results are available, analyze filter blanks for each target metal prior
to emission testing. Quartz fiber filters meeting these requirements are
recommended. However, if glass fiber filters become available which meet
these requirements, they may be used. Filter efficiencies and
unreactiveness to sulfur dioxide (SO2) or sulfur trioxide
(SO3) shall be as described in Section 7.1.1 of Method 5.
7.2.2 Water. To conform to ASTM Specification D1193-77 or 91, Type
II (incorporated by reference--see Sec. 60.17). If necessary, analyze
the water for all target metals prior to field use. All target metals
should be less than 1 ng/ml.
7.2.3 HNO3, Concentrated. Baker Instra-analyzed or
equivalent.
7.2.4 HCl, Concentrated. Baker Instra-analyzed or equivalent.
7.2.5 H2O2, 30 Percent (V/V).
7.2.6 KMnO4.
7.2.7 H2SO4, Concentrated.
7.2.8 Silica Gel and Crushed Ice. Same as Method 5, Sections 7.1.2
and 7.1.4, respectively.
7.3 Pretest Preparation of Sampling Reagents.
7.3.1 HNO3/H2O2 Absorbing Solution,
5 Percent HNO3/10 Percent H2O2. Add
carefully with stirring 50 ml of concentrated HNO3 to a 1000-
ml volumetric flask containing approximately 500 ml of water, and then
add

[[Page 588]]

carefully with stirring 333 ml of 30 percent H2O2.
Dilute to volume with water. Mix well. This reagent shall contain less
than 2 ng/ml of each target metal.
7.3.2 Acidic KMnO4 Absorbing Solution, 4 Percent
KMnO4 (W/V), 10 Percent H2SO4 (V/V).
Prepare fresh daily. Mix carefully, with stirring, 100 ml of
concentrated H2SO4 into approximately 800 ml of
water, and add water with stirring to make a volume of 1 liter: this
solution is 10 percent H2SO4 (V/V). Dissolve, with
stirring, 40 g of KMnO4 into 10 percent
H2SO4 (V/V) and add 10 percent
H2SO4 (V/V) with stirring to make a volume of 1
liter. Prepare and store in glass bottles to prevent degradation. This
reagent shall contain less than 2 ng/ml of Hg.
Precaution: To prevent autocatalytic decomposition of the
permanganate solution, filter the solution through Whatman 541 filter
paper.
7.3.3 HNO3, 0.1 N. Add with stirring 6.3 ml of
concentrated HNO3 (70 percent) to a flask containing
approximately 900 ml of water. Dilute to 1000 ml with water. Mix well.
This reagent shall contain less than 2 ng/ml of each target metal.
7.3.4 HCl, 8 N. Carefully add with stirring 690 ml of concentrated
HCl to a flask containing 250 ml of water. Dilute to 1000 ml with water.
Mix well. This reagent shall contain less than 2 ng/ml of Hg.
7.4 Glassware Cleaning Reagents.
7.4.1 HNO3, Concentrated. Fisher ACS grade or equivalent.
7.4.2 Water. To conform to ASTM Specifications D1193, Type II.
7.4.3 HNO3, 10 Percent (V/V). Add with stirring 500 ml of
concentrated HNO3 to a flask containing approximately 4000 ml
of water. Dilute to 5000 ml with water. Mix well. This reagent shall
contain less than 2 ng/ml of each target metal.
7.5 Sample Digestion and Analysis Reagents. The metals standards,
except Hg, may also be made from solid chemicals as described in
Reference 3 in Section 16.0. Refer to References 1, 2, or 5 in Section
16.0 for additional information on Hg standards. The 1000 [micro]g/ml Hg
stock solution standard may be made according to Section 7.2.7 of Method
101A.
7.5.1 HCl, Concentrated.
7.5.2 HF, Concentrated.
7.5.3 HNO3, Concentrated. Baker Instra-analyzed or
equivalent.
7.5.4 HNO3, 50 Percent (V/V). Add with stirring 125 ml of
concentrated HNO3 to 100 ml of water. Dilute to 250 ml with
water. Mix well. This reagent shall contain less than 2 ng/ml of each
target metal.
7.5.5 HNO3, 5 Percent (V/V). Add with stirring 50 ml of
concentrated HNO3 to 800 ml of water. Dilute to 1000 ml with
water. Mix well. This reagent shall contain less than 2 ng/ml of each
target metal.
7.5.6 Water. To conform to ASTM Specifications D1193, Type II.
7.5.7 Hydroxylamine Hydrochloride and Sodium Chloride Solution. See
Reference 2 In Section 16.0 for preparation.
7.5.8 Stannous Chloride. See Reference 2 in Section 16.0 for
preparation.
7.5.9 KMnO4, 5 Percent (W/V). See Reference 2 in Section
16.0 for preparation.
7.5.10 H2SO4, Concentrated.
7.5.11 Potassium Persulfate, 5 Percent (W/V). See Reference 2 in
Section 16.0 for preparation.
7.5.12 Nickel Nitrate, Ni(N03) 2
6H20.
7.5.13 Lanthanum Oxide, La203.
7.5.14 Hg Standard (AAS Grade), 1000 [micro]g/ml.
7.5.15 Pb Standard (AAS Grade), 1000 [micro]g/ml.
7.5.16 As Standard (AAS Grade), 1000 [micro]g/ml.
7.5.17 Cd Standard (AAS Grade), 1000 [micro]g/ml.
7.5.18 Cr Standard (AAS Grade), 1000 [micro]g/ml.
7.5.19 Sb Standard (AAS Grade), 1000 [micro]g/ml.
7.5.20 Ba Standard (AAS Grade), 1000 [micro]g/ml.
7.5.21 Be Standard (AAS Grade), 1000 [micro]g/ml.
7.5.22 Co Standard (AAS Grade), 1000 [micro]g/ml.
7.5.23 Cu Standard (AAS Grade), 1000 [micro]g/ml.
7.5.24 Mn Standard (AAS Grade), 1000 [micro]g/ml.
7.5.25 Ni Standard (AAS Grade), 1000 [micro]g/ml.
7.5.26 P Standard (AAS Grade), 1000 [micro]g/ml.
7.5.27 Se Standard (AAS Grade), 1000 [micro]g/ml.
7.5.28 Ag Standard (AAS Grade), 1000 [micro]g/ml.
7.5.29 Tl Standard (AAS Grade), 1000 [micro]g/ml.
7.5.30 Zn Standard (AAS Grade), 1000 [micro]g/ml.
7.5.31 Al Standard (AAS Grade), 1000 [micro]g/ml.
7.5.32 Fe Standard (AAS Grade), 1000 [micro]g/ml.
7.5.33 Hg Standards and Quality Control Samples. Prepare fresh
weekly a 10 [micro]g/ml intermediate Hg standard by adding 5 ml of 1000
[micro]g/ml Hg stock solution prepared according to Method 101A to a
500-ml volumetric flask; dilute with stirring to 500 ml by first
carefully adding 20 ml of 15 percent HNO3 and then adding
water to the 500-ml volume. Mix well. Prepare a 200 ng/ml working Hg
standard solution fresh daily: add 5 ml of the 10 [micro]g/ml
intermediate standard to a 250-ml volumetric flask, and dilute to 250 ml
with 5 ml of 4 percent KMnO4, 5 ml of 15 percent
HNO3, and then water. Mix well. Use at least five separate
aliquots of the working

[[Page 589]]

Hg standard solution and a blank to prepare the standard curve. These
aliquots and blank shall contain 0.0, 1.0, 2.0, 3.0, 4.0, and 5.0 ml of
the working standard solution containing 0, 200, 400, 600, 800, and 1000
ng Hg, respectively. Prepare quality control samples by making a
separate 10 [micro]g/ml standard and diluting until in the calibration
range.
7.5.34 ICAP Standards and Quality Control Samples. Calibration
standards for ICAP analysis can be combined into four different mixed
standard solutions as follows:

Mixed Standard Solutions for ICAP Analysis
------------------------------------------------------------------------
Solution Elements
------------------------------------------------------------------------
I................................. As, Be, Cd, Mn, Pb, Se, Zn.
II................................ Ba, Co, Cu, Fe.
III............................... Al, Cr, Ni.
IV................................ Ag, P, Sb, Tl.
------------------------------------------------------------------------

Prepare these standards by combining and diluting the appropriate
volumes of the 1000 [micro]g/ml solutions with 5 percent
HNO3. A minimum of one standard and a blank can be used to
form each calibration curve. However, prepare a separate quality control
sample spiked with known amounts of the target metals in quantities in
the mid-range of the calibration curve. Suggested standard levels are 25
[micro]g/ml for Al, Cr and Pb, 15 [micro]g/ml for Fe, and 10 [micro]g/ml
for the remaining elements. Prepare any standards containing less than 1
[micro]g/ml of metal on a daily basis. Standards containing greater than
1 [micro]g/ml of metal should be stable for a minimum of 1 to 2 weeks.
For ICP-MS, follow Method 6020 in EPA Publication SW-846 Third Edition
(November 1986) including updates I, II, IIA, IIB and III, as
incorporated by reference in Sec. 60.17(i).
7.5.35 GFAAS Standards. Sb, As, Cd, Co, Pb, Se, and Tl. Prepare a 10
[micro]g/ml standard by adding 1 ml of 1000 [micro]g/ml standard to a
100-ml volumetric flask. Dilute with stirring to 100 ml with 10 percent
HNO3. For GFAAS, matrix match the standards. Prepare a 100
ng/ml standard by adding 1 ml of the 10 [micro]g/ml standard to a 100-ml
volumetric flask, and dilute to 100 ml with the appropriate matrix
solution. Prepare other standards by diluting the 100 ng/ml standards.
Use at least five standards to make up the standard curve. Suggested
levels are 0, 10, 50, 75, and 100 ng/ml. Prepare quality control samples
by making a separate 10 [micro]g/ml standard and diluting until it is in
the range of the samples. Prepare any standards containing less than 1
[micro]g/ml of metal on a daily basis. Standards containing greater than
1 [micro]g/ml of metal should be stable for a minimum of 1 to 2 weeks.
7.5.36 Matrix Modifiers.
7.5.36.1 Nickel Nitrate, 1 Percent (V/V). Dissolve 4.956 g of
Ni(N03)2[middot]6H20 or other nickel
compound suitable for preparation of this matrix modifier in
approximately 50 ml of water in a 100-ml volumetric flask. Dilute to 100
ml with water.
7.5.36.2 Nickel Nitrate, 0.1 Percent (V/V). Dilute 10 ml of 1
percent nickel nitrate solution to 100 ml with water. Inject an equal
amount of sample and this modifier into the graphite furnace during
GFAAS analysis for As.
7.5.36.3 Lanthanum. Carefully dissolve 0.5864 g of
La203 in 10 ml of concentrated HN03,
and dilute the solution by adding it with stirring to approximately 50
ml of water. Dilute to 100 ml with water, and mix well. Inject an equal
amount of sample and this modifier into the graphite furnace during
GFAAS analysis for Pb.
7.5.37 Whatman 40 and 541 Filter Papers (or equivalent). For
filtration of digested samples.

8.0 Sample Collection, Preservation, Transport, and Storage

8.1 Sampling. The complexity of this method is such that, to obtain
reliable results, both testers and analysts must be trained and
experienced with the test procedures, including source sampling; reagent
preparation and handling; sample handling; safety equipment and
procedures; analytical calculations; reporting; and the specific
procedural descriptions throughout this method.
8.1.1 Pretest Preparation. Follow the same general procedure given
in Method 5, Section 8.1, except that, unless particulate emissions are
to be determined, the filter need not be desiccated or weighed. First,
rinse all sampling train glassware with hot tap water and then wash in
hot soapy water. Next, rinse glassware three times with tap water,
followed by three additional rinses with water. Then soak all glassware
in a 10 percent (V/V) nitric acid solution for a minimum of 4 hours,
rinse three times with water, rinse a final time with acetone, and allow
to air dry. Cover all glassware openings where contamination can occur
until the sampling train is assembled for sampling.
8.1.2 Preliminary Determinations. Same as Method 5, Section 8.1.2.
8.1.3 Preparation of Sampling Train.
8.1.3.1 Set up the sampling train as shown in Figure 29-1. Follow
the same general procedures given in Method 5, Section 8.3, except place
100 ml of the HNO3/H2O2 solution
(Section 7.3.1 of this method) in each of the second and third impingers
as shown in Figure 29-1. Place 100 ml of the acidic KMnO4
absorbing solution (Section 7.3.2 of this method) in each of the fifth
and sixth impingers as shown in Figure 29-1, and transfer approximately
200 to 300 g of pre-weighed silica gel from its container to the last
impinger. Alternatively, the silica gel may be weighed directly in the
impinger just prior to final train assembly.

[[Page 590]]

8.1.3.2 Based on the specific source sampling conditions, the use of
an empty first impinger can be eliminated if the moisture to be
collected in the impingers will be less than approximately 100 ml.
8.1.3.3 If Hg analysis will not be performed, the fourth, fifth, and
sixth impingers as shown in Figure 29-1 are not required.
8.1.3.4 To insure leak-free sampling train connections and to
prevent possible sample contamination problems, use Teflon tape or other
non-contaminating material instead of silicone grease.
Precaution: Exercise extreme care to prevent contamination within
the train. Prevent the acidic KMnO4 from contacting any
glassware that contains sample material to be analyzed for Mn. Prevent
acidic H2O2 from mixing with the acidic
KMnO4.
8.1.4 Leak-Check Procedures. Follow the leak-check procedures given
in Method 5, Section 8.4.2 (Pretest Leak-Check), Section 8.4.3 (Leak-
Checks During the Sample Run), and Section 8.4.4 (Post-Test Leak-
Checks).
8.1.5 Sampling Train Operation. Follow the procedures given in
Method 5, Section 8.5. When sampling for Hg, use a procedure analogous
to that described in Section 8.1 of Method 101A, 40 CFR Part 61,
Appendix B, if necessary to maintain the desired color in the last
acidified permanganate impinger. For each run, record the data required
on a data sheet such as the one shown in Figure 5-3 of Method 5.
8.1.6 Calculation of Percent Isokinetic. Same as Method 5, Section
12.11.
8.2 Sample Recovery.
8.2.1 Begin cleanup procedures as soon as the probe is removed from
the stack at the end of a sampling period. The probe should be allowed
to cool prior to sample recovery. When it can be safely handled, wipe
off all external particulate matter near the tip of the probe nozzle and
place a rinsed, non-contaminating cap over the probe nozzle to prevent
losing or gaining particulate matter. Do not cap the probe tip tightly
while the sampling train is cooling; a vacuum can form in the filter
holder with the undesired result of drawing liquid from the impingers
onto the filter.
8.2.2 Before moving the sampling train to the cleanup site, remove
the probe from the sampling train and cap the open outlet. Be careful
not to lose any condensate that might be present. Cap the filter inlet
where the probe was fastened. Remove the umbilical cord from the last
impinger and cap the impinger. Cap the filter holder outlet and impinger
inlet. Use non-contaminating caps, whether ground-glass stoppers,
plastic caps, serum caps, or Teflon ^[reg] tape to close these
openings.
8.2.3 Alternatively, the following procedure may be used to
disassemble the train before the probe and filter holder/oven are
completely cooled: Initially disconnect the filter holder outlet/
impinger inlet and loosely cap the open ends. Then disconnect the probe
from the filter holder or cyclone inlet and loosely cap the open ends.
Cap the probe tip and remove the umbilical cord as previously described.
8.2.4 Transfer the probe and filter-impinger assembly to a cleanup
area that is clean and protected from the wind and other potential
causes of contamination or loss of sample. Inspect the train before and
during disassembly and note any abnormal conditions. Take special
precautions to assure that all the items necessary for recovery do not
contaminate the samples. The sample is recovered and treated as follows
(see schematic in Figures 29-2a and 29-2b):
8.2.5 Container No. 1 (Sample Filter). Carefully remove the filter
from the filter holder and place it in its labeled petri dish container.
To handle the filter, use either acid-washed polypropylene or Teflon
coated tweezers or clean, disposable surgical gloves rinsed with water
and dried. If it is necessary to fold the filter, make certain the
particulate cake is inside the fold. Carefully transfer the filter and
any particulate matter or filter fibers that adhere to the filter holder
gasket to the petri dish by using a dry (acid-cleaned) nylon bristle
brush. Do not use any metal-containing materials when recovering this
train. Seal the labeled petri dish.
8.2.6 Container No. 2 (Acetone Rinse). Perform this procedure only
if a determination of particulate emissions is to be made.
Quantitatively recover particulate matter and any condensate from the
probe nozzle, probe fitting, probe liner, and front half of the filter
holder by washing these components with a total of 100 ml of acetone,
while simultaneously taking great care to see that no dust on the
outside of the probe or other surfaces gets in the sample. The use of
exactly 100 ml is necessary for the subsequent blank correction
procedures. Distilled water may be used instead of acetone when approved
by the Administrator and shall be used when specified by the
Administrator; in these cases, save a water blank and follow the
Administrator's directions on analysis.
8.2.6.1 Carefully remove the probe nozzle, and clean the inside
surface by rinsing with acetone from a wash bottle while brushing with a
non-metallic brush. Brush until the acetone rinse shows no visible
particles, then make a final rinse of the inside surface with acetone.
8.2.6.2 Brush and rinse the sample exposed inside parts of the probe
fitting with acetone in a similar way until no visible particles remain.
Rinse the probe liner with acetone by tilting and rotating the probe
while squirting acetone into its upper end so that all inside surfaces
will be wetted with acetone. Allow the acetone to drain from the lower
end into the sample container. A funnel may be used to aid in
transferring liquid washings

[[Page 591]]

to the container. Follow the acetone rinse with a non-metallic probe
brush. Hold the probe in an inclined position, squirt acetone into the
upper end as the probe brush is being pushed with a twisting action
three times through the probe. Hold a sample container underneath the
lower end of the probe, and catch any acetone and particulate matter
which is brushed through the probe until no visible particulate matter
is carried out with the acetone or until none remains in the probe liner
on visual inspection. Rinse the brush with acetone, and quantitatively
collect these washings in the sample container. After the brushing, make
a final acetone rinse of the probe as described above.
8.2.6.3 It is recommended that two people clean the probe to
minimize sample losses. Between sampling runs, keep brushes clean and
protected from contamination. Clean the inside of the front-half of the
filter holder by rubbing the surfaces with a non-metallic brush and
rinsing with acetone. Rinse each surface three times or more if needed
to remove visible particulate. Make a final rinse of the brush and
filter holder. After all acetone washings and particulate matter have
been collected in the sample container, tighten the lid so that acetone
will not leak out when shipped to the laboratory. Mark the height of the
fluid level to determine whether or not leakage occurred during
transport. Clearly label the container to identify its contents.
8.2.7 Container No. 3 (Probe Rinse). Keep the probe assembly clean
and free from contamination during the probe rinse. Rinse the probe
nozzle and fitting, probe liner, and front-half of the filter holder
thoroughly with a total of 100 ml of 0.1 N HNO3, and place
the wash into a sample storage container. Perform the rinses as
applicable and generally as described in Method 12, Section 8.7.1.
Record the volume of the rinses. Mark the height of the fluid level on
the outside of the storage container and use this mark to determine if
leakage occurs during transport. Seal the container, and clearly label
the contents. Finally, rinse the nozzle, probe liner, and front-half of
the filter holder with water followed by acetone, and discard these
rinses.

Note: The use of a total of exactly 100 ml is necessary for the
subsequent blank correction procedures.

8.2.8 Container No. 4 (Impingers 1 through 3, Moisture Knockout
Impinger, when used, HNO3/H2O2
Impingers Contents and Rinses). Due to the potentially large quantity of
liquid involved, the tester may place the impinger solutions from
impingers 1 through 3 in more than one container, if necessary. Measure
the liquid in the first three impingers to within 0.5 ml using a
graduated cylinder. Record the volume. This information is required to
calculate the moisture content of the sampled flue gas. Clean each of
the first three impingers, the filter support, the back half of the
filter housing, and connecting glassware by thoroughly rinsing with 100
ml of 0.1 N HNO3 using the procedure as applicable in Method
12, Section 8.7.3.

Note: The use of exactly 100 ml of 0.1 N HNO3 rinse is
necessary for the subsequent blank correction procedures. Combine the
rinses and impinger solutions, measure and record the final total
volume. Mark the height of the fluid level, seal the container, and
clearly label the contents.

8.2.9 Container Nos. 5A (0.1 N HNO3), 5B
(KMnO4/H2SO4 absorbing solution), and
5C (8 N HCl rinse and dilution).
8.2.9.1 When sampling for Hg, pour all the liquid from the impinger
(normally impinger No. 4) that immediately preceded the two permanganate
impingers into a graduated cylinder and measure the volume to within 0.5
ml. This information is required to calculate the moisture content of
the sampled flue gas. Place the liquid in Container No. 5A. Rinse the
impinger with exactly 100 ml of 0.1 N HNO3 and place this
rinse in Container No. 5A.
8.2.9.2 Pour all the liquid from the two permanganate impingers into
a graduated cylinder and measure the volume to within 0.5 ml. This
information is required to calculate the moisture content of the sampled
flue gas. Place this acidic KMnO4 solution into Container No.
5B. Using a total of exactly 100 ml of fresh acidified KMnO4
solution for all rinses (approximately 33 ml per rinse), rinse the two
permanganate impingers and connecting glassware a minimum of three
times. Pour the rinses into Container No. 5B, carefully assuring
transfer of all loose precipitated materials from the two impingers.
Similarly, using 100 ml total of water, rinse the permanganate impingers
and connecting glass a minimum of three times, and pour the rinses into
Container 5B, carefully assuring transfer of any loose precipitated
material. Mark the height of the fluid level, and clearly label the
contents. Read the Precaution: in Section 7.3.2.

Note: Due to the potential reaction of KMnO4 with acid,
pressure buildup can occur in the sample storage bottles. Do not fill
these bottles completely and take precautions to relieve excess
pressure. A No. 70-72 hole drilled in the container cap and Teflon liner
has been used successfully.

8.2.9.3 If no visible deposits remain after the water rinse, no
further rinse is necessary. However, if deposits remain on the impinger
surfaces, wash them with 25 ml of 8 N HCl, and place the wash in a
separate sample container labeled No. 5C containing 200 ml of water.
First, place 200 ml of water in the container. Then wash the impinger
walls and stem with the HCl by turning the

[[Page 592]]

impinger on its side and rotating it so that the HCl contacts all inside
surfaces. Use a total of only 25 ml of 8 N HCl for rinsing both
permanganate impingers combined. Rinse the first impinger, then pour the
actual rinse used for the first impinger into the second impinger for
its rinse. Finally, pour the 25 ml of 8 N HCl rinse carefully into the
container. Mark the height of the fluid level on the outside of the
container to determine if leakage occurs during transport.
8.2.10 Container No. 6 (Silica Gel). Note the color of the
indicating silica gel to determine whether it has been completely spent
and make a notation of its condition. Transfer the silica gel from its
impinger to its original container and seal it. The tester may use a
funnel to pour the silica gel and a rubber policeman to remove the
silica gel from the impinger. The small amount of particles that might
adhere to the impinger wall need not be removed. Do not use water or
other liquids to transfer the silica gel since weight gained in the
silica gel impinger is used for moisture calculations. Alternatively, if
a balance is available in the field, record the weight of the spent
silica gel (or silica gel plus impinger) to the nearest 0.5 g.
8.2.11 Container No. 7 (Acetone Blank). If particulate emissions are
to be determined, at least once during each field test, place a 100-ml
portion of the acetone used in the sample recovery process into a
container labeled No. 7. Seal the container.
8.2.12 Container No. 8A (0.1 N HNO3 Blank). At least once
during each field test, place 300 ml of the 0.1 N HNO3
solution used in the sample recovery process into a container labeled
No. 8A. Seal the container.
8.2.13 Container No. 8B (Water Blank). At least once during each
field test, place 100 ml of the water used in the sample recovery
process into a container labeled No. 8B. Seal the container.
8.2.14 Container No. 9 (5 Percent HNO3/10 Percent
H2O2 Blank). At least once during each field test,
place 200 ml of the 5 Percent HNO3/10 Percent
H2O2 solution used as the nitric acid impinger
reagent into a container labeled No. 9. Seal the container.
8.2.15 Container No. 10 (Acidified KMnO4 Blank). At least
once during each field test, place 100 ml of the acidified
KMnO4 solution used as the impinger solution and in the
sample recovery process into a container labeled No. 10. Prepare the
container as described in Section 8.2.9.2. Read the Precaution: in
Section 7.3.2 and read the NOTE in Section 8.2.9.2.
8.2.16 Container No. 11 (8 N HCl Blank). At least once during each
field test, place 200 ml of water into a sample container labeled No.
11. Then carefully add with stirring 25 ml of 8 N HCl. Mix well and seal
the container.
8.2.17 Container No. 12 (Sample Filter Blank). Once during each
field test, place into a petri dish labeled No. 12 three unused blank
filters from the same lot as the sampling filters. Seal the petri dish.
8.3 Sample Preparation. Note the level of the liquid in each of the
containers and determine if any sample was lost during shipment. If a
noticeable amount of leakage has occurred, either void the sample or use
methods, subject to the approval of the Administrator, to correct the
final results. A diagram illustrating sample preparation and analysis
procedures for each of the sample train components is shown in Figure
29-3.
8.3.1 Container No. 1 (Sample Filter).
8.3.1.1 If particulate emissions are being determined, first
desiccate the filter and filter catch without added heat (do not heat
the filters to speed the drying) and weigh to a constant weight as
described in Section 11.2.1 of Method 5.
8.3.1.2 Following this procedure, or initially, if particulate
emissions are not being determined in addition to metals analysis,
divide the filter with its filter catch into portions containing
approximately 0.5 g each. Place the pieces in the analyst's choice of
either individual microwave pressure relief vessels or Parr Bombs. Add 6
ml of concentrated HNO3 and 4 ml of concentrated HF to each
vessel. For microwave heating, microwave the samples for approximately
12 to 15 minutes total heating time as follows: heat for 2 to 3 minutes,
then turn off the microwave for 2 to 3 minutes, then heat for 2 to 3
minutes, etc., continue this alternation until the 12 to 15 minutes
total heating time are completed (this procedure should comprise
approximately 24 to 30 minutes at 600 watts). Microwave heating times
are approximate and are dependent upon the number of samples being
digested simultaneously. Sufficient heating is evidenced by sorbent
reflux within the vessel. For conventional heating, heat the Parr Bombs
at 140 [deg]C (285 [deg]F) for 6 hours. Then cool the samples to room
temperature, and combine with the acid digested probe rinse as required
in Section 8.3.3.
8.3.1.3 If the sampling train includes an optional glass cyclone in
front of the filter, prepare and digest the cyclone catch by the
procedures described in Section 8.3.1.2 and then combine the digestate
with the digested filter sample.
8.3.2 Container No. 2 (Acetone Rinse). Note the level of liquid in
the container and confirm on the analysis sheet whether or not leakage
occurred during transport. If a noticeable amount of leakage has
occurred, either void the sample or use methods, subject to the approval
of the Administrator, to correct the final results. Measure the liquid
in this container either volumetrically within 1 ml or gravimetrically
within 0.5 g. Transfer the contents to an acid-cleaned, tared 250-ml
beaker and evaporate to dryness at ambient temperature and pressure. If
particulate

[[Page 593]]

emissions are being determined, desiccate for 24 hours without added
heat, weigh to a constant weight according to the procedures described
in Section 11.2.1 of Method 5, and report the results to the nearest 0.1
mg. Redissolve the residue with 10 ml of concentrated HNO3.
Quantitatively combine the resultant sample, including all liquid and
any particulate matter, with Container No. 3 before beginning Section
8.3.3.
8.3.3 Container No. 3 (Probe Rinse). Verify that the pH of this
sample is 2 or lower. If it is not, acidify the sample by careful
addition with stirring of concentrated HNO3 to pH 2. Use
water to rinse the sample into a beaker, and cover the beaker with a
ribbed watch glass. Reduce the sample volume to approximately 20 ml by
heating on a hot plate at a temperature just below boiling. Digest the
sample in microwave vessels or Parr Bombs by quantitatively transferring
the sample to the vessel or bomb, carefully adding the 6 ml of
concentrated HNO3, 4 ml of concentrated HF, and then
continuing to follow the procedures described in Section 8.3.1.2. Then
combine the resultant sample directly with the acid digested portions of
the filter prepared previously in Section 8.3.1.2. The resultant
combined sample is referred to as ``Sample Fraction 1''. Filter the
combined sample using Whatman 541 filter paper. Dilute to 300 ml (or the
appropriate volume for the expected metals concentration) with water.
This diluted sample is ``Analytical Fraction 1''. Measure and record the
volume of Analytical Fraction 1 to within 0.1 ml. Quantitatively remove
a 50-ml aliquot and label as ``Analytical Fraction 1B''. Label the
remaining 250-ml portion as ``Analytical Fraction 1A''. Analytical
Fraction 1A is used for ICAP or AAS analysis for all desired metals
except Hg. Analytical Fraction 1B is used for the determination of
front-half Hg.
8.3.4 Container No. 4 (Impingers 1-3). Measure and record the total
volume of this sample to within 0.5 ml and label it ``Sample Fraction
2''. Remove a 75- to 100-ml aliquot for Hg analysis and label the
aliquot ``Analytical Fraction 2B''. Label the remaining portion of
Container No. 4 as ``Sample Fraction 2A''. Sample Fraction 2A defines
the volume of Analytical Fraction 2A prior to digestion. All of Sample
Fraction 2A is digested to produce ``Analytical Fraction 2A''.
Analytical Fraction 2A defines the volume of Sample Fraction 2A after
its digestion and the volume of Analytical Fraction 2A is normally 150
ml. Analytical Fraction 2A is analyzed for all metals except Hg. Verify
that the pH of Sample Fraction 2A is 2 or lower. If necessary, use
concentrated HNO3 by careful addition and stirring to lower
Sample Fraction 2A to pH 2. Use water to rinse Sample Fraction 2A into a
beaker and then cover the beaker with a ribbed watchglass. Reduce Sample
Fraction 2A to approximately 20 ml by heating on a hot plate at a
temperature just below boiling. Then follow either of the digestion
procedures described in Sections 8.3.4.1 or 8.3.4.2.
8.3.4.1 Conventional Digestion Procedure. Add 30 ml of 50 percent
HNO3, and heat for 30 minutes on a hot plate to just below
boiling. Add 10 ml of 3 percent H2O2 and heat for
10 more minutes. Add 50 ml of hot water, and heat the sample for an
additional 20 minutes. Cool, filter the sample, and dilute to 150 ml (or
the appropriate volume for the expected metals concentrations) with
water. This dilution produces Analytical Fraction 2A. Measure and record
the volume to within 0.1 ml.
8.3.4.2 Microwave Digestion Procedure. Add 10 ml of 50 percent
HNO3 and heat for 6 minutes total heating time in
alternations of 1 to 2 minutes at 600 Watts followed by 1 to 2 minutes
with no power, etc., similar to the procedure described in Section
8.3.1. Allow the sample to cool. Add 10 ml of 3 percent
H2O2 and heat for 2 more minutes. Add 50 ml of hot
water, and heat for an additional 5 minutes. Cool, filter the sample,
and dilute to 150 ml (or the appropriate volume for the expected metals
concentrations) with water. This dilution produces Analytical Fraction
2A. Measure and record the volume to within 0.1 ml.

Note: All microwave heating times given are approximate and are
dependent upon the number of samples being digested at a time. Heating
times as given above have been found acceptable for simultaneous
digestion of up to 12 individual samples. Sufficient heating is
evidenced by solvent reflux within the vessel.

8.3.5 Container No. 5A (Impinger 4), Container Nos. 5B and 5C
(Impingers 5 and 6). Keep the samples in Containers Nos. 5A, 5B, and 5C
separate from each other. Measure and record the volume of 5A to within
0.5 ml. Label the contents of Container No. 5A to be Analytical Fraction
3A. To remove any brown MnO2 precipitate from the contents of
Container No. 5B, filter its contents through Whatman 40 filter paper
into a 500 ml volumetric flask and dilute to volume with water. Save the
filter for digestion of the brown MnO2 precipitate. Label the
500 ml filtrate from Container No. 5B to be Analytical Fraction 3B.
Analyze Analytical Fraction 3B for Hg within 48 hours of the filtration
step. Place the saved filter, which was used to remove the brown
MnO2 precipitate, into an appropriately sized vented
container, which will allow release of any gases including chlorine
formed when the filter is digested. In a laboratory hood which will
remove any gas produced by the digestion of the MnO2, add 25
ml of 8 N HCl to the filter and allow to digest for a minimum of 24
hours at room temperature. Filter the contents of Container No. 5C
through a Whatman 40 filter into a 500-ml volumetric flask. Then filter

[[Page 594]]

the result of the digestion of the brown MnO2 from Container
No. 5B through a Whatman 40 filter into the same 500-ml volumetric
flask, and dilute and mix well to volume with water. Discard the Whatman
40 filter. Mark this combined 500-ml dilute HCl solution as Analytical
Fraction 3C.
8.3.6 Container No. 6 (Silica Gel). Weigh the spent silica gel (or
silica gel plus impinger) to the nearest 0.5 g using a balance.

9.0 Quality Control

9.1 Field Reagent Blanks, if analyzed. Perform the digestion and
analysis of the blanks in Container Nos. 7 through 12 that were produced
in Sections 8.2.11 through 8.2.17, respectively. For Hg field reagent
blanks, use a 10 ml aliquot for digestion and analysis.
9.1.1 Digest and analyze one of the filters from Container No. 12
per Section 8.3.1, 100 ml from Container No. 7 per Section 8.3.2, and
100 ml from Container No. 8A per Section 8.3.3. This step produces
blanks for Analytical Fractions 1A and 1B.
9.1.2 Combine 100 ml of Container No. 8A with 200 ml from Container
No. 9, and digest and analyze the resultant volume per Section 8.3.4.
This step produces blanks for Analytical Fractions 2A and 2B.
9.1.3 Digest and analyze a 100-ml portion of Container No. 8A to
produce a blank for Analytical Fraction 3A.
9.1.4 Combine 100 ml from Container No. 10 with 33 ml from Container
No. 8B to produce a blank for Analytical Fraction 3B. Filter the
resultant 133 ml as described for Container No. 5B in Section 8.3.5,
except do not dilute the 133 ml. Analyze this blank for Hg within 48 hr
of the filtration step, and use 400 ml as the blank volume when
calculating the blank mass value. Use the actual volumes of the other
analytical blanks when calculating their mass values.
9.1.5 Digest the filter that was used to remove any brown
MnO2 precipitate from the blank for Analytical Fraction 3B by
the same procedure as described in Section 8.3.5 for the similar sample
filter. Filter the digestate and the contents of Container No. 11
through Whatman 40 paper into a 500-ml volumetric flask, and dilute to
volume with water. These steps produce a blank for Analytical Fraction
3C.
9.1.6 Analyze the blanks for Analytical Fraction Blanks 1A and 2A
per Section 11.1.1 and/or Section 11.1.2. Analyze the blanks for
Analytical Fractions 1B, 2B, 3A, 3B, and 3C per Section 11.1.3. Analysis
of the blank for Analytical Fraction 1A produces the front-half reagent
blank correction values for the desired metals except for Hg; Analysis
of the blank for Analytical Fraction 1B produces the front-half reagent
blank correction value for Hg. Analysis of the blank for Analytical
Fraction 2A produces the back-half reagent blank correction values for
all of the desired metals except for Hg, while separate analyses of the
blanks for Analytical Fractions 2B, 3A, 3B, and 3C produce the back-half
reagent blank correction value for Hg.
9.2 Quality Control Samples. Analyze the following quality control
samples.
9.2.1 ICAP and ICP-MS Analysis. Follow the respective quality
control descriptions in Section 8 of Methods 6010 and 6020 in EPA
Publication SW-846 Third Edition (November 1986) including updates I,
II, IIA, IIB and III, as incorporated by reference in Sec. 60.17(i).
For the purposes of a source test that consists of three sample runs,
modify those requirements to include the following: two instrument check
standard runs, two calibration blank runs, one interference check sample
at the beginning of the analysis (analyze by Method of Standard
Additions unless within 25 percent), one quality control sample to check
the accuracy of the calibration standards (required to be within 25
percent of calibration), and one duplicate analysis (required to be
within 20 percent of average or repeat all analyses).
9.2.2 Direct Aspiration AAS and/or GFAAS Analysis for Sb, As, Ba,
Be, Cd, Cu, Cr, Co, Pb, Ni, Mn, Hg, P, Se, Ag, Tl, and Zn. Analyze all
samples in duplicate. Perform a matrix spike on at least one front-half
sample and one back-half sample, or one combined sample. If recoveries
of less than 75 percent or greater than 125 percent are obtained for the
matrix spike, analyze each sample by the Method of Standard Additions.
Analyze a quality control sample to check the accuracy of the
calibration standards. If the results are not within 20 percent, repeat
the calibration.
9.2.3 CVAAS Analysis for Hg. Analyze all samples in duplicate.
Analyze a quality control sample to check the accuracy of the
calibration standards (if not within 15 percent, repeat calibration).
Perform a matrix spike on one sample (if not within 25 percent, analyze
all samples by the Method of Standard Additions). Additional information
on quality control can be obtained from Method 7470 in EPA Publication
SW-846 Third Edition (November 1986) including updates I, II, IIA, IIB
and III, as incorporated by reference in Sec. 60.17(i), or in Standard
Methods for Water and Wastewater Method 303F.

10.0 Calibration and Standardization

Note: Maintain a laboratory log of all calibrations.

10.1 Sampling Train Calibration. Calibrate the sampling train
components according to the indicated sections of Method 5: Probe Nozzle
(Section 10.1); Pitot Tube (Section 10.2); Metering System (Section
10.3); Probe Heater (Section 10.4); Temperature Sensors (Section 10.5);
Leak-Check of the Metering System (Section 8.4.1); and Barometer
(Section 10.6).

[[Page 595]]

10.2 Inductively Coupled Argon Plasma Spectrometer Calibration.
Prepare standards as outlined in Section 7.5. Profile and calibrate the
instrument according to the manufacturer's recommended procedures using
those standards. Check the calibration once per hour. If the instrument
does not reproduce the standard concentrations within 10 percent,
perform the complete calibration procedures. Perform ICP-MS analysis by
following Method 6020 in EPA Publication SW-846 Third Edition (November
1986) including updates I, II, IIA, IIB and III, as incorporated by
reference in Sec. 60.17(i).
10.3 Atomic Absorption Spectrometer--Direct Aspiration AAS, GFAAS,
and CVAAS analyses. Prepare the standards as outlined in Section 7.5 and
use them to calibrate the spectrometer. Calibration procedures are also
outlined in the EPA methods referred to in Table 29-2 and in Method 7470
in EPA Publication SW-846 Third Edition (November 1986) including
updates I, II, IIA, IIB and III, as incorporated by reference in Sec.
60.17(i), or in Standard Methods for Water and Wastewater Method 303F
(for Hg). Run each standard curve in duplicate and use the mean values
to calculate the calibration line. Recalibrate the instrument
approximately once every 10 to 12 samples.

11.0 Analytical Procedure

11.1 Sample Analysis. For each sampling train sample run, seven
individual analytical samples are generated; two for all desired metals
except Hg, and five for Hg. A schematic identifying each sample
container and the prescribed analytical preparation and analysis scheme
is shown in Figure 29-3. The first two analytical samples, labeled
Analytical Fractions 1A and 1B, consist of the digested samples from the
front-half of the train. Analytical Fraction 1A is for ICAP, ICP-MS or
AAS analysis as described in Sections 11.1.1 and 11.1.2, respectively.
Analytical Fraction 1B is for front-half Hg analysis as described in
Section 11.1.3. The contents of the back-half of the train are used to
prepare the third through seventh analytical samples. The third and
fourth analytical samples, labeled Analytical Fractions 2A and 2B,
contain the samples from the moisture removal impinger No. 1, if used,
and HNO3/H2O2 impingers Nos. 2 and 3.
Analytical Fraction 2A is for ICAP, ICP-MS or AAS analysis for target
metals, except Hg. Analytical Fraction 2B is for analysis for Hg. The
fifth through seventh analytical samples, labeled Analytical Fractions
3A, 3B, and 3C, consist of the impinger contents and rinses from the
empty impinger No. 4 and the H2SO4/
KMnO4 Impingers Nos. 5 and 6. These analytical samples are
for analysis for Hg as described in Section 11.1.3. The total back-half
Hg catch is determined from the sum of Analytical Fractions 2B, 3A, 3B,
and 3C. Analytical Fractions 1A and 2A can be combined proportionally
prior to analysis.
11.1.1 ICAP and ICP-MS Analysis. Analyze Analytical Fractions 1A and
2A by ICAP using Method 6010 or Method 200.7 (40 CFR 136, Appendix C).
Calibrate the ICAP, and set up an analysis program as described in
Method 6010 or Method 200.7. Follow the quality control procedures
described in Section 9.2.1. Recommended wavelengths for analysis are as
shown in Table 29-2. These wavelengths represent the best combination of
specificity and potential detection limit. Other wavelengths may be
substituted if they can provide the needed specificity and detection
limit, and are treated with the same corrective techniques for spectral
interference. Initially, analyze all samples for the target metals
(except Hg) plus Fe and Al. If Fe and Al are present, the sample might
have to be diluted so that each of these elements is at a concentration
of less than 50 ppm so as to reduce their spectral interferences on As,
Cd, Cr, and Pb. Perform ICP-MS analysis by following Method 6020 in EPA
Publication SW-846 Third Edition (November 1986) including updates I,
II, IIA, IIB and III, as incorporated by reference in Sec. 60.17(i).

Note: When analyzing samples in a HF matrix, an alumina torch should
be used; since all front-half samples will contain HF, use an alumina
torch.

11.1.2 AAS by Direct Aspiration and/or GFAAS. If analysis of metals
in Analytical Fractions 1A and 2A by using GFAAS or direct aspiration
AAS is needed, use Table 29-3 to determine which techniques and
procedures to apply for each target metal. Use Table 29-3, if necessary,
to determine techniques for minimization of interferences. Calibrate the
instrument according to Section 10.3 and follow the quality control
procedures specified in Section 9.2.2.
11.1.3 CVAAS Hg analysis. Analyze Analytical Fractions 1B, 2B, 3A,
3B, and 3C separately for Hg using CVAAS following the method outlined
in Method 7470 in EPA Publication SW-846 Third Edition (November 1986)
including updates I, II, IIA, IIB and III, as incorporated by reference
in Sec. 60.17(i), or in Standard Methods for Water and Wastewater
Analysis, 15th Edition, Method 303F, or, optionally using Note No. 2 at
the end of this section. Set up the calibration curve (zero to 1000 ng)
as described in Method 7470 or similar to Method 303F using 300-ml BOD
bottles instead of Erlenmeyers. Perform the following for each Hg
analysis. From each original sample, select and record an aliquot in the
size range from 1 ml to 10 ml. If no prior knowledge of the expected
amount of Hg in the sample exists, a 5 ml aliquot is suggested for the
first dilution to 100 ml (see Note No. 1 at end of this section). The
total amount of Hg in the aliquot shall be less than 1 [micro]g and
within the range (zero to 1000

[[Page 596]]

ng) of the calibration curve. Place the sample aliquot into a separate
300-ml BOD bottle, and add enough water to make a total volume of 100
ml. Next add to it sequentially the sample digestion solutions and
perform the sample preparation described in the procedures of Method
7470 or Method 303F. (See Note No. 2 at the end of this section). If the
maximum readings are off-scale (because Hg in the aliquot exceeded the
calibration range; including the situation where only a 1-ml aliquot of
the original sample was digested), then dilute the original sample (or a
portion of it) with 0.15 percent HNO3 (1.5 ml concentrated
HNO3 per liter aqueous solution) so that when a 1- to 10-ml
aliquot of the ``0.15 HNO3 percent dilution of the original
sample'' is digested and analyzed by the procedures described above, it
will yield an analysis within the range of the calibration curve.

Note No. 1: When Hg levels in the sample fractions are below the in-
stack detection limit given in Table 29-1, select a 10 ml aliquot for
digestion and analysis as described.
Note No. 2: Optionally, Hg can be analyzed by using the CVAAS
analytical procedures given by some instrument manufacturer's
directions. These include calibration and quality control procedures for
the Leeman Model PS200, the Perkin Elmer FIAS systems, and similar
models, if available, of other instrument manufacturers. For digestion
and analyses by these instruments, perform the following two steps: (1),
Digest the sample aliquot through the addition of the aqueous
hydroxylamine hydrochloride/sodium chloride solution the same as
described in this section: (The Leeman, Perkin Elmer, and similar
instruments described in this note add automatically the necessary
stannous chloride solution during the automated analysis of Hg.); (2),
Upon completion of the digestion described in (1), analyze the sample
according to the instrument manufacturer's directions. This approach
allows multiple (including duplicate) automated analyses of a digested
sample aliquot.

12.0 Data Analysis and Calculations

12.1 Nomenclature.

A=Analytical detection limit, [micro]g/ml.
B=Liquid volume of digested sample prior to aliquotting for analysis,
ml.
C=Stack sample gas volume, dsm\3\.
Ca1=Concentration of metal in Analytical Fraction 1A as read
from the standard curve, [micro]g/ml.
Ca2=Concentration of metal in Analytical Fraction 2A as read
from the standard curve, ([micro]g/ml).
Cs=Concentration of a metal in the stack gas, mg/dscm.
D=In-stack detection limit, [micro]g/m\3\.
Fa=Aliquot factor, volume of Sample Fraction 2 divided by
volume of Sample Fraction 2A (see Section 8.3.4.)
Fd=Dilution factor (Fd=the inverse of the
fractional portion of the concentrated sample in the solution actually
used in the instrument to produce the reading Ca1. For
example, if a 2 ml aliquot of Analytical Fraction 1A is diluted to 10 ml
to place it in the calibration range, Fd=5).
Hgbh=Total mass of Hg collected in the back-half of the
sampling train, [micro]g.
Hgbh2=Total mass of Hg collected in Sample Fraction 2,
[micro]g.
Hgbh3(A,B,C)=Total mass of Hg collected separately in
Fraction 3A, 3B, or 3C, [micro]g.
Hgbhb=Blank correction value for mass of Hg detected in back-
half field reagent blanks, [micro]g.
Hgfh=Total mass of Hg collected in the front-half of the
sampling train (Sample Fraction 1), [micro]g.
Hgfhb=Blank correction value for mass of Hg detected in
front-half field reagent blank, [micro]g.
Hgt=Total mass of Hg collected in the sampling train,
[micro]g.
Mbh=Total mass of each metal (except Hg) collected in the
back-half of the sampling train (Sample Fraction 2), [micro]g.
Mbhb=Blank correction value for mass of metal detected in
back-half field reagent blank, [micro]g.
Mfh=Total mass of each metal (except Hg) collected in the
front half of the sampling train (Sample Fraction 1), [micro]g.
Mfhb=Blank correction value for mass of metal detected in
front-half field reagent blank, [micro]g.
Mt=Total mass of each metal (separately stated for each
metal) collected in the sampling train, [micro]g.
Mt=Total mass of that metal collected in the sampling train,
[micro]g; (substitute Hgt for Mt for the
Hg calculation).
Qbh2=Quantity of Hg, [micro]g, TOTAL in the ALIQUOT of
Analytical Fraction 2B selected for digestion and analysis . NOTE: For
example, if a 10 ml aliquot of Analytical Fraction 2B is taken and
digested and analyzed (according to Section 11.1.3 and its NOTES Nos. 1
and 2), then calculate and use the total amount of Hg in the 10 ml
aliquot for Qbh2.
Qbh3(A,B,C)=Quantity of Hg, [micro]g, TOTAL, separately, in
the ALIQUOT of Analytical Fraction 3A, 3B, or 3C selected for digestion
and analysis (see NOTES in Sections 12.7.1 and 12.7.2 describing the
quantity ``Q'' and calculate similarly).
Qfh=Quantity of Hg, [micro]g, TOTAL in the ALIQUOT of
Analytical Fraction 1B selected for digestion and analysis. NOTE: For
example, if a 10 ml aliquot of Analytical Fraction 1B is taken and
digested and analyzed (according to Section 11.1.3 and its NOTES Nos. 1

[[Page 597]]

and 2), then calculate and use the total amount of Hg in the 10 ml
aliquot for Qfh.
Va=Total volume of digested sample solution (Analytical
Fraction 2A), ml (see Section 8.3.4.1 or 8.3.4.2, as applicable).
Vf1B=Volume of aliquot of Analytical Fraction 1B analyzed,
ml. NOTE: For example, if a 1 ml aliquot of Analytical Fraction 1B was
diluted to 50 ml with 0.15 percent HNO3 as described in
Section 11.1.3 to bring it into the proper analytical range, and then 1
ml of that 50-ml was digested according to Section 11.1.3 and analyzed,
Vf1B would be 0.02 ml.
Vf2B=Volume of Analytical Fraction 2B analyzed, ml. NOTE: For
example, if 1 ml of Analytical Fraction 2B was diluted to 10 ml with
0.15 percent HNO3 as described in Section 11.1.3 to bring it
into the proper analytical range, and then 5 ml of that 10 ml was
analyzed, Vf2B would be 0.5 ml.
Vf3(A,B,C)=Volume, separately, of Analytical Fraction 3A, 3B,
or 3C analyzed, ml (see previous notes in Sections 12.7.1 and 12.7.2,
describing the quantity ``V'' and calculate similarly).
Vm(std)=Volume of gas sample as measured by the dry gas
meter, corrected to dry standard conditions, dscm.
Vsoln,1=Total volume of digested sample solution (Analytical
Fraction 1), ml.
Vsoln,1=Total volume of Analytical Fraction 1, ml.
Vsoln,2=Total volume of Sample Fraction 2, ml.
Vsoln,3(A,B,C)=Total volume, separately, of Analytical
Fraction 3A, 3B, or 3C, ml.
K4=10^-\3\ mg/[micro]g.

12.2 Dry Gas Volume. Using the data from this test, calculate
Vm(std), the dry gas sample volume at standard conditions as
outlined in Section 12.3 of Method 5.
12.3 Volume of Water Vapor and Moisture Content. Using the total
volume of condensate collected during the source sampling, calculate the
volume of water vapor Vw(std) and the moisture content
Bws of the stack gas. Use Equations 5-2 and 5-3 of Method 5.
12.4 Stack Gas Velocity. Using the data from this test and Equation
2-9 of Method 2, calculate the average stack gas velocity.
12.5 In-Stack Detection Limits. Calculate the in-stack method
detection limits shown in Table 29-4 using the conditions described in
Section 13.3.1 as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.439

12.6 Metals (Except Hg) in Source Sample.
12.6.1 Analytical Fraction 1A, Front-Half, Metals (except Hg).
Calculate separately the amount of each metal collected in Sample
Fraction 1 of the sampling train using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.440

Note: If Analytical Fractions 1A and 2A are combined, use
proportional aliquots. Then make appropriate changes in Equations 29-2
through 29-4 to reflect this approach.

12.6.2 Analytical Fraction 2A, Back-Half, Metals (except Hg).
Calculate separately the amount of each metal collected in Fraction 2 of
the sampling train using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.441

12.6.3 Total Train, Metals (except Hg). Calculate the total amount
of each of the quantified metals collected in the sampling train as
follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.442

Note: If the measured blank value for the front half
(Mfhb) is in the range 0.0 to ``A'' [micro]g (where ``A''
[micro]g equals the value determined by multiplying 1.4 [micro]g/in.2
times the actual area in in.2 of the sample filter), use Mfhb
to correct the emission sample value (Mfh); if
Mfhb exceeds ``A'' [micro]g, use the greater of I or II:
I. ``A'' [micro]g.
II. The lesser of (a) Mfhb, or (b) 5 percent of
Mfh. If the measured blank value for the back-half
(Mbhb) is in the range 0.0 to 1 [micro]g, use Mbhb
to correct the emission sample value (Mbh); if
Mbhb exceeds 1 [micro]g, use the greater of I or II:
I. 1 [micro]g.
II. The lesser of (a) Mbhb, or (b) 5 percent of
Mbh.

12.7 Hg in Source Sample.
12.7.1 Analytical Fraction 1B; Front-Half Hg. Calculate the amount
ofHg collected in the front-half, Sample Fraction 1, of the sampling
train by using Equation 29-5:
[GRAPHIC] [TIFF OMITTED] TR17OC00.443

12.7.2 Analytical Fractions 2B, 3A, 3B, and 3C; Back Half Hg.
12.7.2.1 Calculate the amount of Hg collected in Sample Fraction 2
by using Equation 29-6:

[[Page 598]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.444

12.7.2.2 Calculate each of the back-half Hg values for Analytical
Fractions 3A, 3B, and 3C by using Equation 29-7:
[GRAPHIC] [TIFF OMITTED] TR17OC00.445

12.7.2.3 Calculate the total amount of Hg collected in the back-half
of the sampling train by using Equation 29-8:
[GRAPHIC] [TIFF OMITTED] TR17OC00.446

12.7.3 Total Train Hg Catch. Calculate the total amount of Hg
collected in the sampling train by using Equation 29-9:
[GRAPHIC] [TIFF OMITTED] TR17OC00.447

Note: If the total of the measured blank values (Hgfhb +
Hgbhb) is in the range of 0.0 to 0.6 [micro]g, then use the
total to correct the sample value (Hgfh + Hgbh);
if it exceeds 0.6 [micro]g, use the greater of I. or II:
I. 0.6 [micro]g.
II. The lesser of (a) (Hgfhb + Hgbhb), or (b)
5 percent of the sample value (Hgfh + Hgbh).

12.8 Individual Metal Concentrations in Stack Gas. Calculate the
concentration of each metal in the stack gas (dry basis, adjusted to
standard conditions) by using Equation 29-10:
[GRAPHIC] [TIFF OMITTED] TR17OC00.448

12.9 Isokinetic Variation and Acceptable Results. Same as Method 5,
Sections 12.11 and 12.12, respectively.

13.0 Method Performance

13.1 Range. For the analysis described and for similar analyses, the
ICAP response is linear over several orders of magnitude. Samples
containing metal concentrations in the nanograms per ml (ng/ml) to
micrograms per ml ([micro]g/ml) range in the final analytical solution
can be analyzed using this method. Samples containing greater than
approximately 50 [micro]g/ml As, Cr, or Pb should be diluted to that
level or lower for final analysis. Samples containing greater than
approximately 20 [micro]g/ml of Cd should be diluted to that level
before analysis.
13.2 Analytical Detection Limits.

Note: See Section 13.3 for the description of in-stack detection
limits.

13.2.1 ICAP analytical detection limits for the sample solutions
(based on SW-846, Method 6010) are approximately as follows: Sb (32 ng/
ml), As (53 ng/ml), Ba (2 ng/ml), Be (0.3 ng/ml), Cd (4 ng/ml), Cr (7
ng/ml), Co (7 ng/ml), Cu (6 ng/ml), Pb (42 ng/ml), Mn (2 ng/ml), Ni (15
ng/ml), P (75 ng/ml), Se (75 ng/ml), Ag (7 ng/ml), Tl (40 ng/ml), and Zn
(2 ng/ml). ICP-MS analytical detection limits (based on SW-846, Method
6020) are lower generally by a factor of ten or more. Be is lower by a
factor of three. The actual sample analytical detection limits are
sample dependent and may vary due to the sample matrix.
13.2.2 The analytical detection limits for analysis by direct
aspiration AAS (based on SW-846, Method 7000 series) are approximately
as follows: Sb (200 ng/ml), As (2 ng/ml), Ba (100 ng/ml), Be (5 ng/ml),
Cd (5 ng/ml), Cr (50 ng/ml), Co (50 ng/ml), Cu (20 ng/ml), Pb (100 ng/
ml), Mn (10 ng/ml), Ni (40 ng/ml), Se (2 ng/ml), Ag (10 ng/ml), Tl (100
ng/ml), and Zn (5 ng/ml).
13.2.3 The detection limit for Hg by CVAAS (on the resultant volume
of the digestion of the aliquots taken for Hg analyses)

[[Page 599]]

can be approximately 0.02 to 0.2 ng/ml, depending upon the type of CVAAS
analytical instrument used. 13.2.4 The use of GFAAS can enhance the
detection limits compared to direct aspiration AAS as follows: Sb (3 ng/
ml), As (1 ng/ml), Be (0.2 ng/ml), Cd (0.1 ng/ml), Cr (1 ng/ml), Co (1
ng/ml), Pb (1 ng/ml), Se (2 ng/ml), and Tl (1 ng/ml).
13.3 In-stack Detection Limits.
13.3.1 For test planning purposes in-stack detection limits can be
developed by using the following information: (1) The procedures
described in this method, (2) the analytical detection limits described
in Section 13.2 and in SW-846,(3) the normal volumes of 300 ml
(Analytical Fraction 1) for the front-half and 150 ml (Analytical
Fraction 2A) for the back-half samples, and (4) a stack gas sample
volume of 1.25 m\3\. The resultant in-stack method detection limits for
the above set of conditions are presented in Table 29-1 and were
calculated by using Eq. 29-1 shown in Section 12.5.
13.3.2 To ensure optimum precision/resolution in the analyses, the
target concentrations of metals in the analytical solutions should be at
least ten times their respective analytical detection limits. Under
certain conditions, and with greater care in the analytical procedure,
these concentrations can be as low as approximately three times the
respective analytical detection limits without seriously impairing the
precision of the analyses. On at least one sample run in the source
test, and for each metal analyzed, perform either repetitive analyses,
Method of Standard Additions, serial dilution, or matrix spike addition,
etc., to document the quality of the data.
13.3.3 Actual in-stack method detection limits are based on actual
source sampling parameters and analytical results as described above. If
required, the method in-stack detection limits can be improved over
those shown in Table 29-1 for a specific test by either increasing the
sampled stack gas volume, reducing the total volume of the digested
samples, improving the analytical detection limits, or any combination
of the three. For extremely low levels of Hg only, the aliquot size
selected for digestion and analysis can be increased to as much as 10
ml, thus improving the in-stack detection limit by a factor of ten
compared to a 1 ml aliquot size.
13.3.3.1 A nominal one hour sampling run will collect a stack gas
sampling volume of about 1.25 m\3\. If the sampling time is increased to
four hours and 5 m\3\ are collected, the in-stack method detection
limits would be improved by a factor of four compared to the values
shown in Table 29-1.
13.3.3.2 The in-stack detection limits assume that all of the sample
is digested and the final liquid volumes for analysis are the normal
values of 300 ml for Analytical Fraction 1, and 150 ml for Analytical
Fraction 2A. If the volume of Analytical Fraction 1 is reduced from 300
to 30 ml, the in-stack detection limits for that fraction of the sample
would be improved by a factor of ten. If the volume of Analytical
Fraction 2A is reduced from 150 to 25 ml, the in-stack detection limits
for that fraction of the sample would be improved by a factor of six.
Matrix effect checks are necessary on sample analyses and typically are
of much greater significance for samples that have been concentrated to
less than the normal original sample volume. Reduction of Analytical
Fractions 1 and 2A to volumes of less than 30 and 25 ml, respectively,
could interfere with the redissolving of the residue and could increase
interference by other compounds to an intolerable level.
13.3.3.3 When both of the modifications described in Sections
13.3.3.1 and 13.3.3.2 are used simultaneously on one sample, the
resultant improvements are multiplicative. For example, an increase in
stack gas volume by a factor of four and a reduction in the total liquid
sample digested volume of both Analytical Fractions 1 and 2A by a factor
of six would result in an improvement by a factor of twenty-four of the
in-stack method detection limit.
13.4 Precision. The precision (relative standard deviation) for each
metal detected in a method development test performed at a sewage sludge
incinerator were found to be as follows:

Sb (12.7 percent), As (13.5 percent), Ba (20.6 percent), Cd (11.5
percent), Cr (11.2 percent), Cu (11.5 percent), Pb (11.6 percent), P
(14.6 percent), Se (15.3 percent), Tl (12.3 percent), and Zn (11.8
percent). The precision for Ni was 7.7 percent for another test
conducted at a source simulator. Be, Mn, and Ag were not detected in the
tests. However, based on the analytical detection limits of the ICAP for
these metals, their precisions could be similar to those for the other
metals when detected at similar levels.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Method 303F in Standard Methods for the Examination of Water
Wastewater, 15th Edition, 1980. Available from the American Public
Health Association, 1015 18th Street N.W., Washington, D.C. 20036.
2. EPA Methods 6010, 6020, 7000, 7041, 7060, 7131, 7421, 7470, 7740,
and 7841, Test Methods for Evaluating Solid Waste: Physical/Chemical
Methods. SW-846, Third Edition, November 1986, with updates I, II, IIA,
IIB and III. Office of Solid Waste and Emergency Response, U. S.
Environmental Protection Agency, Washington, DC 20460.

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3. EPA Method 200.7, Code of Federal Regulations, Title 40, Part
136, Appendix C. July 1, 1987.
4. EPA Methods 1 through 5, Code of Federal Regulations, Title 40,
Part 60, Appendix A, July 1, 1991.
5. EPA Method 101A, Code of Federal Regulations, Title 40, Part 61,
Appendix B, July 1, 1991.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

Table 29-1--In Stack Method Detection Limits (ug/m\3\) for the Front-Half, the Back Half, and the Total Sampling
Train Using ICAP, GFAAS, and CVAAS
----------------------------------------------------------------------------------------------------------------
Front-half: Back-half:
Metal probe and Back-half: impringers 4- Total train
filter impinters 1-3 6 \a\
----------------------------------------------------------------------------------------------------------------
Antimony........................................ \1\ 7.7 (0.7) \1\ 3.8 (0.4) .............. \1\ 11.5 (1.1)
Arsenic......................................... \1\ 12.7 (0.3) \1\ 6.4 (0.1) .............. \1\ 19.1 (0.4)
Barium.......................................... 0.5 0.3 .............. 0.8
Beryllium....................................... \1\ 0.07 \1\ 0.04 .............. \1\ 0.11
(0.05) (0.03) (0.08)
Cadmium......................................... \1\ 1.0 (0.02) \1\ 0.5 (0.01) .............. \1\ 1.5 (0.03)
Chromium........................................ \1\ 1.7 (0.2) \1\ 0.8 (0.1) .............. \1\ 2.5 (0.3)
Cobalt.......................................... \1\ 1.7 (0.2) \1\ 0.8 (0.1) .............. \1\ 2.5 (0.3)
Copper.......................................... 1.4 0.7 .............. 2.1
Lead............................................ \1\ 10.1 (0.2) \1\ 5.0 (0.1) .............. \1\ 15.1 (0.3)
Manganese....................................... \1\ 0.5 (0.2) \1\ 0.2 (0.1) .............. \1\ 0.7 (0.3)
Mercury......................................... \2\ 0.06 \2\ 0.3 \2\ 0.2 \2\ 0.56
Nickel.......................................... 3.6 1.8 .............. 5.4
Phosphorus...................................... 18 9 .............. 27
Selenium........................................ \1\ 18 (0.5) \1\ 9 (0.3) .............. \1\ 27 (0.8)
Silver.......................................... 1.7 0.9 (0.7) .............. 2.6
Thallium........................................ \1\ 9.6 (0.2) \1\ 4.8 (0.1) .............. \1\ 14.4 (0.3)
Zinc............................................ 0.5 0.3 .............. 0.8
----------------------------------------------------------------------------------------------------------------
\a\ Mercury analysis only.
\1\ Detection limit when analyzed by ICAP or GFAAS as shown in parentheses (see Section 11.1.2).
\2\ Detection limit when anaylzed by CVAAS, estimated for Back-half and Total Train. See Sections 13.2 and
11.1.3. Note: Actual method in-stack detection limits may vary from these values, as described in Section
13.3.3.

Table 29-2--Recommended Wavelengths for ICAP Analysis
------------------------------------------------------------------------
Wavelength
Analyte (nm)
------------------------------------------------------------------------
Aluminum (Al)........................................... 308.215
Antimony (Sb)........................................... 206.833
Arsenic (As)............................................ 193.696
Barium (Ba)............................................. 455.403
Beryllium (Be).......................................... 313.042
Cadmium (Cd)............................................ 226.502
Chromium (Cr)........................................... 267.716
Cobalt (Co)............................................. 228.616
Copper (Cu)............................................. 328.754
Iron (Fe)............................................... 259.940
Lead (Pb)............................................... 220.353
Manganese (Mn).......................................... 257.610
Nickel (Ni)............................................. 231.604
Phosphorus (P).......................................... 214.914
Selenium (Se)........................................... 196.026
Silver (Ag)............................................. 328.068
Thallium (T1)........................................... 190,864
Zinc (Zn)............................................... 213,856
------------------------------------------------------------------------

[[Page 601]]

Table 29-3--Applicable Techniques, Methods and Minimization of Interferences for AAS Analysis
----------------------------------------------------------------------------------------------------------------
Interferences
Metal Technique SW-846 \1\ Wavelength ----------------------------------------------
Methods No. (nm) Cause Minimization
----------------------------------------------------------------------------------------------------------------
Fe............... Aspiration.......... 7380 248.3 Contamination...... Great care taken to
avoid contamination.
Pb............... Aspiration.......... 7420 283.3 217.0 nm alternate. Background correction
required.
Pb............... Furnace............. 7421 283.3 Poor recoveries.... Matrix modifier, add 10
[micro]l of phosphorus
acid to 1 ml of
prepared sample in
sampler cup.
Mn............... Aspiration.......... 7460 279.5 403.1 nm alternate. Background correction
required.
Ni............... Aspiration.......... 7520 232.0 352.4 nm alternate Background correction
Fe, Co, and Cr. required. Matrix
Nonlinear response. matching or nitrous-
oxide/acetylene flame
Sample dilution or use
352.3 nm line
Se............... Furnace............. 7740 196.0 Volatility......... Spike samples and
reference materials and
add nickel nitrate to
minimize
volatilization.
Adsorption & Background correction is
scatter. required and Zeeman
background correction
can be useful.
Ag............... Aspiration.......... 7760 328.1 Adsorption & Background correction is
scatter AgCl required. Avoid
insoluble. hydrochloric acid
unless silver is in
solution as a chloride
complex. Sample and
standards monitored for
aspiration rate.
Tl............... Aspiration.......... 7840 276.8 Background correction is
required. Hydrochloric
acid should not be
used.
Tl............... Furnace............. 7841 276.8 Hydrochloric acid Background correction is
or chloride. required. Verify that
losses are not
occurring for
volatilization by
spiked samples or
standard addition;
Palladium is a suitable
matrix modifier.
Zn............... Aspiration.......... 7950 213.9 High Si, Cu, & P Strontium removes Cu and
Contamination. phosphate.
Great care taken to
avoid contamination.
Sb............... Aspiration.......... 7040 217.6 1000 mg/ml Pb, Ni, Use secondary wavelength
Cu, or acid. of 231.1 nm; match
sample & standards acid
concentration or use
nitrous oxide/acetylene
flame.
Sb............... Furnace............. 7041 217.6 High Pb............ Secondary wavelength or
Zeeman correction.
As............... Furnace............. 7060 193.7 Arsenic Spike samples and add
Volatilization nickel nitrate solution
Aluminum. to digestates prior to
analysis. Use Zeeman
background correction.
Ba............... Aspiration.......... 7080 553.6
Calcium............
Barium Ionization.. High hollow cathode
current and narrow band
set.
2 ml of KCl per 100 m1
of sample.
Be............... Aspiration.......... 7090 234.9 500 ppm Al. High Mg Add 0.1% fluoride.
and Si.
Be............... Furnace............. 7091 234.9 Be in optical path. Optimize parameters to
minimize effects.
Cd............... Aspiration.......... 7130 228.8 Absorption and Background correction is
light scattering. required.
Cd............... Furnace............. 7131 228.8 As above........... As above.
Excess Chloride.... Ammonium phosphate used
................... as a matrix modifier.
Pipet Tips......... Use cadmium-free tips.
Cr............... Aspiration.......... 7190 357.9 Alkali metal....... KCl ionization
suppressant in samples
and standards--Consult
mfgs' literature.
Co............... Furnace............. 7201 240.7 Excess chloride.... Use Method of Standard
Additions.
Cr............... Furnace............. 7191 357.9 200 mg/L Ca and P.. All calcium nitrate for
a know constant effect
and to eliminate effect
of phosphate.

[[Page 602]]

Cu............... Aspiration.......... 7210 324.7 Absorption and Consult manufacturer's
Scatter. manual.
----------------------------------------------------------------------------------------------------------------
\1\ Refer to EPA publication SW-846 (Reference 2 in Section 16.0).

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[GRAPHIC] [TIFF OMITTED] TR17OC00.449

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[GRAPHIC] [TIFF OMITTED] TR17OC00.450

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[GRAPHIC] [TIFF OMITTED] TR17OC00.451

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[GRAPHIC] [TIFF OMITTED] TR17OC00.452

[36 FR 24877, Dec. 23, 1971]

Editorial Note: For Federal Register citations affecting part 60,
appendix A-8, see the List of CFR Sections Affected, which appears in
the Finding Aids section of the printed volume and on GPO Access.

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