[[pp. 62143-62192]] Amendments for Testing and Monitoring Provisions

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

[Federal Register: October 17, 2000 (Volume 65, Number 201)]
[Rules and Regulations]
[Page 62143-62192]
From the Federal Register Online via GPO Access [wais.access.gpo.gov]
[DOCID:fr17oc00-18]

[[Continued from page 62142]]

[[Page 62143]]

are not available. The instrument relative error shall be
10 percent of the certified value of the audit gas.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Installation and Measurement Location Specifications. Install
the CEMs in a location where the measurements are representative of the
source emissions. Consider other factors, such as ease of access for
calibration and maintenance purposes. The location should not be close
to air in-leakages. The sampling location should be at least two
equivalent duct diameters downstream from the nearest control device,
point of pollutant generation, or other point at which a change in the
pollutant concentration or emission rate occurs. The location should be
at least 0.5 diameter upstream from the exhaust or control device. To
calculate equivalent duct diameter, see Section 12.2 of Method 1 (40
CFR Part 60, Appendix A). Sampling locations not conforming to the
requirements in this section may be used if necessary upon approval of
the Administrator.
8.2 Pretest Preparation Period. Using the procedures described in
Method 18
(40 CFR Part 60, Appendix A), perform initial tests to determine GC
conditions that provide good resolution and minimum analysis time for
compounds of interest. Resolution interferences that may occur can be
eliminated by appropriate GC column and detector choice or by shifting
the retention times through changes in the column flow rate and the use
of temperature programming.
8.3 7-Day Calibration Error (CE) Test Period. At the beginning of
each 24-hour period, set the initial instrument setpoints by conducting
a multi-point calibration for each compound. The multi-point
calibration shall meet the requirements in Section 13.3. Throughout the
24-hour period, sample and analyze the stack gas at the sampling
intervals prescribed in the regulation or permit. At the end of the 24
hour period, inject the three calibration gases for each compound in
triplicate and determine the average instrument response. Determine the
CE for each pollutant at each level using the equation in Section 9-2.
Each CE shall be 10 percent. Repeat this procedure six
more times for a total of 7 consecutive days.
8.4 Performance Audit Test Periods. Conduct the performance audit
once during the initial 7-day CE test and quarterly thereafter. Sample
and analyze the EPA audit gas(es) (or the gas mixture prepared by EPA's
traceability protocol if an EPA audit gas is not available) three
times. Calculate the average instrument response. Report the audit
results as part of the reporting requirements in the appropriate
regulation or permit (if using a gas mixture, report the certified
cylinder concentration of each pollutant).
8.5 Reporting. Follow the reporting requirements of the applicable
regulation or permit. If the reporting requirements include the results
of this performance specification, summarize in tabular form the
results of the CE tests. Include all data sheets, calculations, CEMS
data records, performance audit results, and calibration gas
concentrations and certifications.

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization

10.1 Initial Multi-Point Calibration. After initial startup of the
GC, after routine maintenance or repair, or at least once per month,
conduct a multi-point calibration of the GC for each target analyte.
The multi-point calibration for each analyte shall meet the
requirements in Section 13.3.
10.2 Daily Calibration. Once every 24 hours, analyze the mid-level
calibration standard for each analyte in triplicate. Calculate the
average instrument response for each analyte. The average instrument
response shall not vary more than 10 percent from the certified
concentration value of the cylinder for each analyte. If the difference
between the analyzer response and the cylinder concentration for any
target compound is greater than 10 percent, immediately inspect the
instrument making any necessary adjustments, and conduct an initial
multi-point calibration as described in Section 10.1.

11.0 Analytical Procedure. Sample Collection and Analysis Are
Concurrent for This Performance Specification (See Section 8.0)

12.0 Calculations and Data Analysis

12.1 Nomenclature.

Cm = average instrument response, ppm.
Ca = cylinder gas value, ppm.
F = Flow rate of stack gas through sampling system, in Liters/min.
n = Number of measurement points.
r2 = Coefficient of determination.
V = Sample system volume, in Liters, which is the volume inside the
sample probe and tubing leading from the stack to the sampling loop.
x = CEMS response.
y = Actual value of calibration standard.
12.2 Coefficient of Determination. Calculate r2 using
linear regression analysis and the average concentrations obtained at
three calibration points as shown in Equation 9-1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.461

12.3 Calibration Error Determination. Determine the percent
calibration error (CE) at each concentration for each pollutant using
the following equation.
[GRAPHIC] [TIFF OMITTED] TR17OC00.462

12.4 Sampling System Time Constant (T).
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13.0 Method Performance

13.1 Calibration Error (CE). The CEMS must allow the determination
of CE at all three calibration levels. The average CEMS calibration
response must not differ by more than 10 percent of calibration gas
value at each level after each 24-hour period of the initial test.
13.2 Calibration Precision and Linearity. For each triplicate
injection at each concentration level for each target analyte, any one
injection shall not deviate more than 5 percent from the average
concentration measured at that level. The linear regression curve for
each organic compound at all three levels shall have an r2
0.995 (using Equation 9-1).
13.3 Measurement Frequency. The sample to be analyzed shall flow
continuously through the sampling system. The sampling system time

[[Page 62144]]

constant shall be 5 minutes or the sampling frequency
specified in the applicable regulation, whichever is less. Use Equation
9-3 to determine T. The analytical system shall be capable of measuring
the effluent stream at the frequency specified in the appropriate
regulation or permit.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References. [Reserved]

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

218. In Part 60, Appendix B is amended by adding Performance
Specification 15 as follows:

Appendix B--Performance Specifications

* * * * *

Performance Specification 15--Performance Specification for
Extractive FTIR Continuous Emissions Monitor Systems in Stationary
Sources

1.0 Scope and Application

1.1 Analytes. This performance specification is applicable for
measuring all hazardous air pollutants (HAPs) which absorb in the
infrared region and can be quantified using Fourier Transform Infrared
Spectroscopy (FTIR), as long as the performance criteria of this
performance specification are met. This specification is to be used for
evaluating FTIR continuous emission monitoring systems for measuring
HAPs regulated under Title III of the 1990 Clean Air Act Amendments.
This specification also applies to the use of FTIR CEMs for measuring
other volatile organic or inorganic species.
1.2 Applicability. A source which can demonstrate that the
extractive FTIR system meets the criteria of this performance
specification for each regulated pollutant may use the FTIR system to
continuously monitor for the regulated pollutants.

2.0 Summary of Performance Specification

For compound-specific sampling requirements refer to FTIR sampling
methods (e.g., reference 1). For data reduction procedures and
requirements refer to the EPA FTIR Protocol (reference 2), hereafter
referred to as the ``FTIR Protocol.'' This specification describes
sampling and analytical procedures for quality assurance. The infrared
spectrum of any absorbing compound provides a distinct signature. The
infrared spectrum of a mixture contains the superimposed spectra of
each mixture component. Thus, an FTIR CEM provides the capability to
continuously measure multiple components in a sample using a single
analyzer. The number of compounds that can be speciated in a single
spectrum depends, in practice, on the specific compounds present and
the test conditions.

3.0 Definitions

For a list of definitions related to FTIR spectroscopy refer to
Appendix A of the FTIR Protocol. Unless otherwise specified,
spectroscopic terms, symbols and equations in this performance
specification are taken from the FTIR Protocol or from documents cited
in the Protocol. Additional definitions are given below.
3.1 FTIR Continuous Emission Monitoring System (FTIR CEM).
3.1.1 FTIR System. Instrument to measure spectra in the mid-
infrared spectral region (500 to 4000 cm-1). It contains an
infrared source, interferometer, sample gas containment cell, infrared
detector, and computer. The interferometer consists of a beam splitter
that divides the beam into two paths, one path a fixed distance and the
other a variable distance. The computer is equipped with software to
run the interferometer and store the raw digitized signal from the
detector (interferogram). The software performs the mathematical
conversion (the Fourier transform) of the interferogram into a spectrum
showing the frequency dependent sample absorbance. All spectral data
can be stored on computer media.
3.1.2 Gas Cell. A gas containment cell that can be evacuated. It
contains the sample as the infrared beam passes from the
interferometer, through the sample, and to the detector. The gas cell
may have multi-pass mirrors depending on the required detection
limit(s) for the application.
3.1.3 Sampling System. Equipment used to extract sample from the
test location and transport the gas to the FTIR analyzer. Sampling
system components include probe, heated line, heated non-reactive pump,
gas distribution manifold and valves, flow measurement devices and any
sample conditioning systems.
3.2 Reference CEM. An FTIR CEM, with sampling system, that can be
used for comparison measurements.
3.3 Infrared Band (also Absorbance Band or Band). Collection of
lines arising from rotational transitions superimposed on a vibrational
transition. An infrared absorbance band is analyzed to determine the
analyte concentration.
3.4 Sample Analysis. Interpreting infrared band shapes,
frequencies, and intensities to obtain sample component concentrations.
This is usually performed by a software routine using a classical least
squares (cls), partial least squares (pls), or K- or P- matrix method.
3.5 (Target) Analyte. A compound whose measurement is required,
usually to some established limit of detection and analytical
uncertainty.
3.6 Interferant. A compound in the sample matrix whose infrared
spectrum overlaps at least part of an analyte spectrum complicating the
analyte measurement. The interferant may not prevent the analyte
measurement, but could increase the analytical uncertainty in the
measured concentration. Reference spectra of interferants are used to
distinguish the interferant bands from the analyte bands. An
interferant for one analyte may not be an interferant for other
analytes.
3.7 Reference Spectrum. Infrared spectra of an analyte, or
interferant, prepared under controlled, documented, and reproducible
laboratory conditions (see Section 4.6 of the FTIR Protocol). A
suitable library of reference spectra can be used to measure target
analytes in gas samples.
3.8 Calibration Spectrum. Infrared spectrum of a compound suitable
for characterizing the FTIR instrument configuration (Section 4.5 in
the FTIR Protocol).
3.9 One hundred percent line. A double beam transmittance spectrum
obtained by combining two successive background single beam spectra.
Ideally, this line is equal to 100 percent transmittance (or zero
absorbance) at every point in the spectrum. The zero absorbance line is
used to measure the RMS noise of the system.
3.10 Background Deviation. Any deviation (from 100 percent) in the
one hundred percent line (or from zero absorbance). Deviations greater
than 5 percent in any analytical region are unacceptable.
Such deviations indicate a change in the instrument throughput relative
to the single-beam background.
3.11 Batch Sampling. A gas cell is alternately filled and
evacuated. A Spectrum of each filled cell (one discreet sample) is
collected and saved.
3.12 Continuous Sampling. Sample is continuously flowing through a
gas cell. Spectra of the flowing sample are collected at regular
intervals.
3.13 Continuous Operation. In continuous operation an FTIR CEM
system, without user intervention, samples flue gas, records spectra of
samples, saves the spectra to a disk, analyzes the spectra for the
target

[[Page 62145]]

analytes, and prints concentrations of target analytes to a computer
file. User intervention is permitted for initial set-up of sampling
system, initial calibrations, and periodic maintenance.
3.14 Sampling Time. In batch sampling--the time required to fill
the cell with flue gas. In continuous sampling--the time required to
collect the infrared spectrum of the sample gas.
3.15 PPM-Meters. Sample concentration expressed as the
concentration-path length product, ppm (molar) concentration multiplied
by the path length of the FTIR gas cell. Expressing concentration in
these units provides a way to directly compare measurements made using
systems with different optical configurations. Another useful
expression is (ppm-meters)/K, where K is the absolute temperature of
the sample in the gas cell.
3.16 CEM Measurement Time Constant. The Time Constant (TC, minutes
for one cell volume to flow through the cell) determines the minimum
interval for complete removal of an analyte from the FTIR cell. It
depends on the sampling rate (Rs in Lpm), the FTIR cell
volume (Vcell in L) and the chemical and physical properties
of an analyte.
[GRAPHIC] [TIFF OMITTED] TR17OC00.464

For example, if the sample flow rate (through the FTIR cell) is 5 Lpm
and the cell volume is 7 liters, then TC is equal to 1.4 minutes (0.71
cell volumes per minute). This performance specification defines 5 * TC
as the minimum interval between independent samples.
3.17 Independent Measurement. Two independent measurements are
spectra of two independent samples. Two independent samples are
separated by, at least 5 cell volumes. The interval between independent
measurements depends on the cell volume and the sample flow rate
(through the cell). There is no mixing of gas between two independent
samples. Alternatively, estimate the analyte residence time
empirically: (1) Fill cell to ambient pressure with a (known analyte
concentration) gas standard, (2) measure the spectrum of the gas
standard, (3) purge the cell with zero gas at the sampling rate and
collect a spectrum every minute until the analyte standard is no longer
detected spectroscopically. If the measured time corresponds to less
than 5 cell volumes, use 5 * TC as the minimum interval between
independent measurements. If the measured time is greater than 5 * TC,
then use this time as the minimum interval between independent
measurements.
3.18 Test Condition. A period of sampling where all process, and
sampling conditions, and emissions remain constant and during which a
single sampling technique and a single analytical program are used. One
Run may include results for more than one test condition. Constant
emissions means that the composition of the emissions remains
approximately stable so that a single analytical program is suitable
for analyzing all of the sample spectra. A greater than two-fold change
in analyte or interferant concentrations or the appearance of
additional compounds in the emissions, may constitute a new test
condition and may require modification of the analytical program.
3.19 Run. A single Run consists of spectra (one spectrum each) of
at least 10 independent samples over a minimum of one hour. The
concentration results from the spectra can be averaged together to give
a run average for each analyte measured in the test run.

4.0 Interferences

Several compounds, including water, carbon monoxide, and carbon
dioxide, are known interferences in the infrared region in which the
FTIR instrument operates. Follow the procedures in the FTIR protocol
for subtracting or otherwise dealing with these and other
interferences.

5.0 Safety

The procedures required under this performance specification may
involve hazardous materials, operations, and equipment. This
performance specification may not address all of the safety problems
associated with these procedures. It is the responsibility of the user
to establish appropriate safety and health practices and determine the
applicable regulatory limitations prior to performing these procedures.
The CEMS users manual and materials recommended by this performance
specification should be consulted for specific precautions to be taken.

6.0 Equipment and Supplies

6.1 Installation of sampling equipment should follow requirements
of FTIR test Methods such as references 1 and 3 and the EPA FTIR
Protocol (reference 2). Select test points where the gas stream
composition is representative of the process emissions. If comparing to
a reference method, the probe tips for the FTIR CEM and the RM should
be positioned close together using the same sample port if possible.
6.2 FTIR Specifications. The FTIR CEM must be equipped with
reference spectra bracketing the range of path length-concentrations
(absorbance intensities) to be measured for each analyte. The effective
concentration range of the analyzer can be adjusted by changing the
path length of the gas cell or by diluting the sample. The optical
configuration of the FTIR system must be such that maximum absorbance
of any target analyte is no greater than 1.0 and the minimum absorbance
of any target analyte is at least 10 times the RMSD noise in the
analytical region. For example, if the measured RMSD in an analytical
region is equal to 10-3, then the peak analyte absorbance is
required to be at least 0.01. Adequate measurement of all of the target
analytes may require changing path lengths during a run, conducting
separate runs for different analytes, diluting the sample, or using
more than one gas cell.
6.3 Data Storage Requirements. The system must have sufficient
capacity to store all data collected in one week of routine sampling.
Data must be stored to a write-protected medium, such as write-once-
read-many (WORM) optical storage medium or to a password protected
remote storage location. A back-up copy of all data can be temporarily
saved to the computer hard drive. The following items must be stored
during testing.
At least one sample interferogram per sampling Run or one
interferogram per hour, whichever is greater. This assumes that no
sampling or analytical conditions have changed during the run.
All sample absorbance spectra (about 12 per hr, 288 per
day).
All background spectra and interferograms (variable, but
about 5 per day).
All CTS spectra and interferograms (at least 2 each 24
hour period).
Documentation showing a record of resolution, path length,
apodization, sampling time, sampling conditions, and test conditions
for all sample, CTS, calibration, and background spectra.
Using a resolution of 0.5 cm-1, with analytical range of
3500 cm-1, assuming about 65 Kbytes per spectrum and 130 Kb
per interferogram, the storage requirement is about 164 Mb for one week
of continuous sampling. Lower spectral resolution requires less storage
capacity. All of the above data must be stored for at least two weeks.
After two weeks, storage requirements include: (1) all analytical
results (calculated concentrations), (2) at least 1 sample spectrum
with corresponding background and sample interferograms for each test
condition, (3) CTS and calibration spectra with at least one
interferogram for CTS and all interferograms for calibrations, (4) a

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record of analytical input used to produce results, and (5) all other
documentation. These data must be stored according to the requirements
of the applicable regulation.

7.0 Reagents and Standards [Reserved]

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

9.0 Quality Control

These procedures shall be used for periodic quarterly or semiannual
QA/QC checks on the operation of the FTIR CEM. Some procedures test
only the analytical program and are not intended as a test of the
sampling system.
9.1 Audit Sample. This can serve as a check on both the sampling
system and the analytical program.
9.1.1 Sample Requirements. The audit sample can be a mixture or a
single component. It must contain target analyte(s) at approximately
the expected flue gas concentration(s). If possible, each mixture
component concentration should be NIST traceable ( 2
percent accuracy). If a cylinder mixture standard(s) cannot be
obtained, then, alternatively, a gas phase standard can be generated
from a condensed phase analyte sample. Audit sample contents and
concentrations are not revealed to the FTIR CEM operator until after
successful completion of procedures in 5.3.2.
9.1.2 Test Procedure. An audit sample is obtained from the
Administrator. Spike the audit sample using the analyte spike procedure
in Section 11. The audit sample is measured directly by the FTIR system
(undiluted) and then spiked into the effluent at a known dilution
ratio. Measure a series of spiked and unspiked samples using the same
procedures as those used to analyze the stack gas. Analyze the results
using Sections 12.1 and 12.2. The measured concentration of each
analyte must be within 5 percent of the expected
concentration (plus the uncertainty), i.e., the calculated correction
factor must be within 0.93 and 1.07 for an audit with an analyte
uncertainty of 2 percent.
9.2 Audit Spectra. Audit spectra can be used to test the
analytical program of the FTIR CEM, but provide no test of the sampling
system.
9.2.1 Definition and Requirements. Audit spectra are absorbance
spectra that; (1) have been well characterized, and (2) contain
absorbance bands of target analyte(s) and potential interferants at
intensities equivalent to what is expected in the source effluent.
Audit spectra are provided by the administrator without identifying
information. Methods of preparing Audit spectra include; (1)
mathematically adding sample spectra or adding reference and
interferant spectra, (2) obtaining sample spectra of mixtures prepared
in the laboratory, or (3) they may be sample spectra collected
previously at a similar source. In the last case it must be
demonstrated that the analytical results are correct and reproducible.
A record associated with each Audit spectrum documents its method of
preparation. The documentation must be sufficient to enable an
independent analyst to reproduce the Audit spectra.
9.2.2 Test Procedure. Audit spectra concentrations are measured
using the FTIR CEM analytical program. Analytical results must be
within 5 percent of the certified audit concentration for
each analyte (plus the uncertainty in the audit concentration). If the
condition is not met, demonstrate how the audit spectra are
unrepresentative of the sample spectra. If the audit spectra are
representative, modify the FTIR CEM analytical program until the test
requirement is met. Use the new analytical program in subsequent FTIR
CEM analyses of effluent samples.
9.3 Submit Spectra For Independent Analysis. This procedure tests
only the analytical program and not the FTIR CEM sampling system. The
analyst can submit FTIR CEM spectra for independent analysis by EPA.
Requirements for submission include; (1) three representative
absorbance spectra (and stored interferograms) for each test period to
be reviewed, (2) corresponding CTS spectra, (3) corresponding
background spectra and interferograms, (4) spectra of associated spiked
samples if applicable, and (5) analytical results for these sample
spectra. The analyst will also submit documentation of process times
and conditions, sampling conditions associated with each spectrum, file
names and sampling times, method of analysis and reference spectra
used, optical configuration of FTIR CEM including cell path length and
temperature, spectral resolution and apodization used for every
spectrum. Independent analysis can also be performed on site in
conjunction with the FTIR CEM sampling and analysis. Sample spectra are
stored on the independent analytical system as they are collected by
the FTIR CEM system. The FTIR CEM and the independent analyses are then
performed separately. The two analyses will agree to within
120 percent for each analyte using the procedure in Section
12.3. This assumes both analytical routines have properly accounted for
differences in optical path length, resolution, and temperature between
the sample spectra and the reference spectra.

10.0 Calibration and Standardization

10.1 Calibration Transfer Standards. For CTS requirements see
Section 4.5 of the FTIR Protocol. A well characterized absorbance band
in the CTS gas is used to measure the path length and line resolution
of the instrument. The CTS measurements made at the beginning of every
24 hour period must agree to within 5 percent after
correction for differences in pressure.
Verify that the frequency response of the instrument and CTS
absorbance intensity are correct by comparing to other CTS spectra or
by referring to the literature.
10.2 Analyte Calibration. If EPA library reference spectra are not
available, use calibration standards to prepare reference spectra
according to Section 6 of the FTIR Protocol. A suitable set of analyte
reference data includes spectra of at least 2 independent samples at
each of at least 2 different concentrations. The concentrations bracket
a range that includes the expected analyte absorbance intensities. The
linear fit of the reference analyte band areas must have a fractional
calibration uncertainty (FCU in Appendix F of the FTIR Protocol) of no
greater than 10 percent. For requirements of analyte standards refer to
Section 4.6 of the FTIR Protocol.
10.3 System Calibration. The calibration standard is introduced at
a point on the sampling probe. The sampling system is purged with the
calibration standard to verify that the absorbance measured in this way
is equal to the absorbance in the analyte calibration. Note that the
system calibration gives no indication of the ability of the sampling
system to transport the target analyte(s) under the test conditions.
10.4 Analyte Spike. The target analyte(s) is spiked at the outlet
of the sampling probe, upstream of the particulate filter, and combined
with effluent at a ratio of about 1 part spike to 9 parts effluent. The
measured absorbance of the spike is compared to the expected absorbance
of the spike plus the analyte concentration already in the effluent.
This measures sampling system bias, if any, as distinguished from
analyzer bias. It is important that spiked sample pass through all of
the sampling system components before analysis.
10.5 Signal-to-Noise Ratio (S/N). The measure of S/N in this
performance specification is the root-mean-square (RMS) noise level as
given in Appendix

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C of the FTIR Protocol. The RMS noise level of a contiguous segment of
a spectrum is defined as the RMS difference (RMSD) between the n
contiguous absorbance values (Ai) which form the segment and
the mean value (AM) of that segment.
[GRAPHIC] [TIFF OMITTED] TR17OC00.465

A decrease in the S/N may indicate a loss in optical throughput, or
detector or interferometer malfunction.
10.6 Background Deviation. The 100 percent baseline must be
between 95 and 105 percent transmittance (absorbance of 0.02 to -0.02)
in every analytical region. When background deviation exceeds this
range, a new background spectrum must be collected using nitrogen or
other zero gas.
10.7 Detector Linearity. Measure the background and CTS at three
instrument aperture settings; one at the aperture setting to be used in
the testing, and one each at settings one half and twice the test
aperture setting. Compare the three CTS spectra. CTS band areas should
agree to within the uncertainty of the cylinder standard. If test
aperture is the maximum aperture, collect CTS spectrum at maximum
aperture, then close the aperture to reduce the IR through-put by half.
Collect a second background and CTS at the smaller aperture setting and
compare the spectra as above. Instead of changing the aperture neutral
density filters can be used to attenuate the infrared beam. Set up the
FTIR system as it will be used in the test measurements. Collect a CTS
spectrum. Use a neutral density filter to attenuate the infrared beam
(either immediately after the source or the interferometer) to
approximately \1/2\ its original intensity. Collect a second CTS
spectrum. Use another filter to attenuate the infrared beam to
approximately \1/4\ its original intensity. Collect a third background
and CTS spectrum. Compare the CTS spectra as above. Another check on
linearity is to observe the single beam background in frequency regions
where the optical configuration is known to have a zero response.
Verify that the detector response is ``flat'' and equal to zero in
these regions. If detector response is not linear, decrease aperture,
or attenuate the infrared beam. Repeat the linearity check until system
passes the requirement.

11.0 Analytical Procedure

11.1 Initial Certification. First, perform the evaluation
procedures in Section 6.0 of the FTIR Protocol. The performance of an
FTIR CEM can be certified upon installation using EPA Method 301 type
validation (40 CFR, Part 63, Appendix A), or by comparison to a
reference Method if one exists for the target analyte(s). Details of
each procedure are given below. Validation testing is used for initial
certification upon installation of a new system. Subsequent performance
checks can be performed with more limited analyte spiking. Performance
of the analytical program is checked initially, and periodically as
required by EPA, by analyzing audit spectra or audit gases.
11.1.1 Validation. Use EPA Method 301 type sampling (reference 4,
Section 5.3 of Method 301) to validate the FTIR CEM for measuring the
target analytes. The analyte spike procedure is as follows: (1) a known
concentration of analyte is mixed with a known concentration of a non-
reactive tracer gas, (2) the undiluted spike gas is sent directly to
the FTIR cell and a spectrum of this sample is collected, (3) pre-heat
the spiked gas to at least the sample line temperature, (4) introduce
spike gas at the back of the sample probe upstream of the particulate
filter, (5) spiked effluent is carried through all sampling components
downstream of the probe, (6) spike at a ratio of roughly 1 part spike
to 9 parts flue gas (or more dilute), (7) the spike-to-flue gas ratio
is estimated by comparing the spike flow to the total sample flow, and
(8) the spike ratio is verified by comparing the tracer concentration
in spiked flue gas to the tracer concentration in undiluted spike gas.
The analyte flue gas concentration is unimportant as long as the spiked
component can be measured and the sample matrix (including
interferences) is similar to its composition under test conditions.
Validation can be performed using a single FTIR CEM analyzing sample
spectra collected sequentially. Since flue gas analyte (unspiked)
concentrations can vary, it is recommended that two separate sampling
lines (and pumps) are used; one line to carry unspiked flue gas and the
other line to carry spiked flue gas. Even with two sampling lines the
variation in unspiked concentration may be fast compared to the
interval between consecutive measurements. Alternatively, two FTIR CEMs
can be operated side-by-side, one measuring spiked sample, the other
unspiked sample. In this arrangement spiked and unspiked measurements
can be synchronized to minimize the affect of temporal variation in the
unspiked analyte concentration. In either sampling arrangement, the
interval between measured concentrations used in the statistical
analysis should be, at least, 5 cell volumes (5 * TC in equation 1). A
validation run consists of, at least, 24 independent analytical
results, 12 spiked and 12 unspiked samples. See Section 3.17 for
definition of an ``independent'' analytical result. The results are
analyzed using Sections 12.1 and 12.2 to determine if the measurements
passed the validation requirements. Several analytes can be spiked and
measured in the same sampling run, but a separate statistical analysis
is performed for each analyte. In lieu of 24 independent measurements,
averaged results can be used in the statistical analysis. In this
procedure, a series of consecutive spiked measurements are combined
over a sampling period to give a single average result. The related
unspiked measurements are averaged in the same way. The minimum 12
spiked and 12 unspiked result averages are obtained by averaging
measurements over subsequent sampling periods of equal duration. The
averaged results are grouped together and statistically analyzed using
Section 12.2.
11.1.1.1 Validation with a Single Analyzer and Sampling Line. If
one sampling line is used, connect the sampling system components and
purge the entire sampling system and cell with at least 10 cell volumes
of sample gas. Begin sampling by collecting spectra of 2 independent
unspiked samples. Introduce the spike gas into the back of the probe,
upstream of the particulate filter. Allow 10 cell volumes of spiked
flue gas to purge the cell and sampling system. Collect spectra of 2
independent spiked samples. Turn off the spike flow and allow 10 cell
volumes of unspiked flue gas to purge the FTIR cell and sampling
system. Repeat this procedure 6 times until the 24 samples are
collected. Spiked and unspiked samples can also be measured in groups
of 4 instead of in pairs. Analyze the results using Sections 12.1 and
12.2. If the statistical analysis passes the validation criteria, then
the validation is completed. If the results do not pass the validation,
the cause may be that temporal variations in the analyte sample gas
concentration are fast relative to the interval between measurements.
The difficulty may be avoided by: (1) Averaging the measurements over
long sampling periods and using the averaged results in the statistical
analysis, (2) modifying the sampling system to reduce TC by, for
example, using a smaller volume cell or increasing the sample flow
rate, (3) using two sample lines (4) use two analyzers to perform
synchronized

[[Page 62148]]

measurements. This performance specification permits modifications in
the sampling system to minimize TC if the other requirements of the
validation sampling procedure are met.
11.1.1.2 Validation With a Single Analyzer and Two Sampling Lines.
An alternative sampling procedure uses two separate sample lines, one
carrying spiked flue gas, the other carrying unspiked gas. A valve in
the gas distribution manifold allows the operator to choose either
sample. A short heated line connects the FTIR cell to the 3-way valve
in the manifold. Both sampling lines are continuously purged. Each
sample line has a rotameter and a bypass vent line after the rotameter,
immediately upstream of the valve, so that the spike and unspiked
sample flows can each be continuously monitored. Begin sampling by
collecting spectra of 2 independent unspiked samples. Turn the sampling
valve to close off the unspiked gas flow and allow the spiked flue gas
to enter the FTIR cell. Isolate and evacuate the cell and fill with the
spiked sample to ambient pressure. (While the evacuated cell is
filling, prevent air leaks into the cell by making sure that the spike
sample rotameter always indicates that a portion of the flow is
directed out the by-pass vent.) Open the cell outlet valve to allow
spiked sample to continuously flow through the cell. Measure spectra of
2 independent spiked samples. Repeat this procedure until at least 24
samples are collected.
11.1.1.3 Synchronized Measurements With Two Analyzers. Use two
FTIR analyzers, each with its own cell, to perform synchronized spiked
and unspiked measurements. If possible, use a similar optical
configuration for both systems. The optical configurations are compared
by measuring the same CTS gas with both analyzers. Each FTIR system
uses its own sampling system including a separate sampling probe and
sampling line. A common gas distribution manifold can be used if the
samples are never mixed. One sampling system and analyzer measures
spiked effluent. The other sampling system and analyzer measures
unspiked flue gas. The two systems are synchronized so that each
measures spectra at approximately the same times. The sample flow rates
are also synchronized so that both sampling rates are approximately the
same (TC1 TC2 in equation 1). Start
both systems at the same time. Collect spectra of at least 12
independent samples with each (spiked and unspiked) system to obtain
the minimum 24 measurements. Analyze the analytical results using
Sections 12.1 and 12.2. Run averages can be used in the statistical
analysis instead of individual measurements.
11.1.1.4 Compare to a Reference Method (RM). Obtain EPA approval
that the method qualifies as an RM for the analyte(s) and the source to
be tested. Follow the published procedures for the RM in preparing and
setting up equipment and sampling system, performing measurements, and
reporting results. Since FTIR CEMS have multicomponent capability, it
is possible to perform more than one RM simultaneously, one for each
target analyte. Conduct at least 9 runs where the FTIR CEM and the RM
are sampling simultaneously. Each Run is at least 30 minutes long and
consists of spectra of at least 5 independent FTIR CEM samples and the
corresponding RM measurements. If more than 9 runs are conducted, the
analyst may eliminate up to 3 runs from the analysis if at least 9 runs
are used.
11.1.1.4.1 RMs Using Integrated Sampling. Perform the RM and FTIR
CEM sampling simultaneously. The FTIR CEM can measure spectra as
frequently as the analyst chooses (and should obtain measurements as
frequently as possible) provided that the measurements include spectra
of at least 5 independent measurements every 30 minutes. Concentration
results from all of the FTIR CEM spectra within a run may be averaged
for use in the statistical comparison even if all of the measurements
are not independent. When averaging the FTIR CEM concentrations within
a run, it is permitted to exclude some measurements from the average
provided the minimum of 5 independent measurements every 30 minutes are
included: The Run average of the FTIR CEM measurements depends on both
the sample flow rate and the measurement frequency (MF). The run
average of the RM using the integrated sampling method depends
primarily on its sampling rate. If the target analyte concentration
fluctuates significantly, the contribution to the run average of a
large fluctuation depends on the sampling rate and measurement
frequency, and on the duration and magnitude of the fluctuation. It is,
therefore, important to carefully select the sampling rate for both the
FTIR CEM and the RM and the measurement frequency for the FTIR CEM. The
minimum of 9 run averages can be compared according to the relative
accuracy test procedure in Performance Specification 2 for
SO2 and NOx CEMs (40 CFR, Part 60, App. B).
11.1.1.4.2 RMs Using a Grab Sampling Technique. Synchronize the RM
and FTIR CEM measurements as closely as possible. For a grab sampling
RM record the volume collected and the exact sampling period for each
sample. Synchronize the FTIR CEM so that the FTIR measures a spectrum
of a similar cell volume at the same time as the RM grab sample was
collected. Measure at least 5 independent samples with both the FTIR
CEM and the RM for each of the minimum 9 Runs. Compare the Run
concentration averages by using the relative accuracy analysis
procedure in 40 CFR, Part 60, App. B.
11.1.1.4.3 Continuous Emission Monitors (CEMs) as RMs. If the RM
is a CEM, synchronize the sampling flow rates of the RM and the FTIR
CEM. Each run is at least 1-hour long and consists of at least 10 FTIR
CEM measurements and the corresponding 10 RM measurements (or
averages). For the statistical comparison use the relative accuracy
analysis procedure in 40 CFR, Part 60, App. B. If the RM time constant
is \1/2\ the FTIR CEM time constant, brief fluctuations in analyte
concentrations which are not adequately measured with the slower FTIR
CEM time constant can be excluded from the run average along with the
corresponding RM measurements. However, the FTIR CEM run average must
still include at least 10 measurements over a 1-hr period.

12.0 Calculations and Data Analysis

12.1 Spike Dilution Ratio, Expected Concentration. The Method 301
bias is calculated as follows.
[GRAPHIC] [TIFF OMITTED] TR17OC00.466

Where:

B = Bias at the spike level
Sm = Mean of the observed spiked sample concentrations
Mm = Mean of the observed unspiked sample concentrations
CS = Expected value of the spiked concentration.

The CS is determined by comparing the SF6 tracer
concentration in undiluted spike gas to the SF6 tracer
concentrations in the spiked samples;
[GRAPHIC] [TIFF OMITTED] TR17OC00.467

The expected concentration (CS) is the measured concentration of the
analyte in undiluted spike gas divided by the dilution factor
[GRAPHIC] [TIFF OMITTED] TR17OC00.468

Where:

[[Page 62149]]

[anal]dir=The analyte concentration in undiluted spike gas
measured directly by filling the FTIR cell with the spike gas.

If the bias is statistically significant (Section 12.2), Method 301
requires that a correction factor, CF, be multiplied by the analytical
results, and that 0.7 CF 1.3.
[GRAPHIC] [TIFF OMITTED] TR17OC00.469

12.2 Statistical Analysis of Validation Measurements. Arrange the
independent measurements (or measurement averages) as in Table 1. More
than 12 pairs of measurements can be analyzed. The statistical analysis
follows EPA Method 301, Section 6.3. Section 12.1 of this performance
specification shows the calculations for the bias, expected spike
concentration, and correction factor. This Section shows the
determination of the statistical significance of the bias. Determine
the statistical significance of the bias at the 95 percent confidence
level by calculating the t-value for the set of measurements. First,
calculate the differences, di, for each pair of spiked and
each pair of unspiked measurements. Then calculate the standard
deviation of the spiked pairs of measurements.
[GRAPHIC] [TIFF OMITTED] TR17OC00.470

Where:

di = The differences between pairs of spiked measurements.
SDs = The standard deviation in the di values.
n = The number of spiked pairs, 2n=12 for the minimum of 12 spiked and
12 unspiked measurements.

Calculate the relative standard deviation, RSD, using SDs
and the mean of the spiked concentrations, Sm. The RSD must
be 50%.
[GRAPHIC] [TIFF OMITTED] TR17OC00.471

Repeat the calculations in equations 7 and 8 to determine
SDu and RSD, respectively, for the unspiked samples.
Calculate the standard deviation of the mean using SDs and
SDu from equation 7.
[GRAPHIC] [TIFF OMITTED] TR17OC00.472

The t-statistic is calculated as follows to test the bias for
statistical significance;
[GRAPHIC] [TIFF OMITTED] TR17OC00.473

where the bias, B, and the correction factor, CF, are given in Section
12.1. For 11 degrees of freedom, and a one-tailed distribution, Method
301 requires that t 2.201. If the t-statistic indicates the
bias is statistically significant, then analytical measurements must be
multiplied by the correction factor. There is no limitation on the
number of measurements, but there must be at least 12 independent
spiked and 12 independent unspiked measurements. Refer to the t-
distribution (Table 2) at the 95 percent confidence level and
appropriate degrees of freedom for the critical t-value.

16.0 References

1. Method 318, 40 CFR, Part 63, Appendix A (Draft),
``Measurement of Gaseous Formaldehyde, Phenol and Methanol Emissions
by FTIR Spectroscopy,'' EPA Contract No. 68D20163, Work Assignment
2-18, February, 1995.

[[Page 62150]]

2. ``EPA Protocol for the Use of Extractive Fourier Transform
Infrared (FTIR) Spectrometry in Analyses of Gaseous Emissions from
Stationary Industrial Sources,'' February, 1995.
3. ``Measurement of Gaseous Organic and Inorganic Emissions by
Extractive FTIR Spectroscopy,'' EPA Contract No. 68-D2-0165, Work
Assignment 3-08.
4. ``Method 301--Field Validation of Pollutant Measurement
Methods from Various Waste Media,'' 40 CFR 63, App A.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

Table 1.--Arrangement of Validation Measurements for Statistical Analysis
----------------------------------------------------------------------------------------------------------------
Measurement (or average) Time Spiked (ppm) di spiked Unspiked (ppm) di unspiked
----------------------------------------------------------------------------------------------------------------
1........................... S1 U1
-------------------------------------------------------------- -----------------
2........................... S2 S2-S1 U2 U2-U1
----------------------------------------------------------------------------------------------------------------
3........................... S3 U3
-------------------------------------------------------------- -----------------
4........................... S4 S4-S3 U4 U4-U3
----------------------------------------------------------------------------------------------------------------
5........................... S5 U5
-------------------------------------------------------------- -----------------
6........................... S6 S6-S5 U6 U6-U5
----------------------------------------------------------------------------------------------------------------
7........................... S7 U7
-------------------------------------------------------------- -----------------
8........................... S8 S8-S7 U8 U8-U7
----------------------------------------------------------------------------------------------------------------
9........................... S9 U9
-------------------------------------------------------------- -----------------
10.......................... S10 S10-S9 U10 U10-U9
----------------------------------------------------------------------------------------------------------------
11.......................... S11 U11
-------------------------------------------------------------- -----------------
12.......................... S12 S12-S11 U12 U12-U11
----------------------------------------------------------------------------------------------------------------
Average ->.................. Sm Mm
----------------------------------------------------------------------------------------------------------------

Table 2.--t=Values
--------------------------------------------------------------------------------------------------------------------------------------------------------
n-1a t-value n-1a t-value n-1a t-value n-1a t-value
--------------------------------------------------------------------------------------------------------------------------------------------------------
11 2.201 17 2.110 23 2.069 29 2.045
12 2.179 18 2.101 24 2.064 30 2.042
13 2.160 19 2.093 25 2.060 40 2.021
14 2.145 20 2.086 26 2.056 60 2.000
15 2.131 21 2.080 27 2.052 120 1.980
16 2.120 22 2.074 28 2.048 8 1.960
--------------------------------------------------------------------------------------------------------------------------------------------------------
(a)n is the number of independent pairs of measurements (a pair consists of one spiked and its corresponding unspiked measurement). Either discreet
(independent) measurements in a single run, or run averages can be used.

* * * * *

PART 61--NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS

1. The authority citation for Part 61 continues to read as follows:
42 U.S.C. 7401, 7412, 7413, 7414, 7416, 7601, and 7602.

2. In Sec. 61.18, paragraph (a) is revised to read as follows:

Sec. 61.18 Incorporation by reference.

* * * * *
(a) The following materials are available for purchase from at
least one of the following addresses: American Society for Testing and
Materials (ASTM), 1916 Race Street, Philadelphia, PA 19103; or
University Microfilms International, 300 North Zeeb Road, Ann Arbor, MI
48106.
(1) ASTM D737-75, Standard Test Method for Air Permeability of
Textile Fabrics, incorporation by reference (IBR) approved January 27,
1983 for Sec. 61.23(a).
(2) ASTM D835-85, Standard Specification for Refined Benzene-485,
IBR approved September 14, 1989 for Sec. 61.270(a).
(3) ASTM D836-84, Standard Specification for Industrial Grade
Benzene, IBR approved September 14, 1989 for Sec. 61.270(a).
(4) ASTM D1193-77, 91, Standard Specification for Reagent Water,
IBR approved for Appendix B: Method 101, Section 7.1.1; Method 101A,
Section 7.1.1; and Method 104, Section 7.1; Method 108, Section 7.1.3;
Method 108A, Section 7.1.1; Method 108B, Section 7.1.1; Method 108C,
Section 7.1.1; and Method 111, Section 7.3.
(5) ASTM D2267-68, 78, 88, Aromatics in Light Naphthas and Aviation
Gasoline by Gas Chromatography, IBR approved September 30, 1986, for
Sec. 61.67(h)(1).
(6) ASTM D2359-85a, 93, Standard Specification for Refined Benzene-
535, IBR approved September 14, 1989 for Sec. 61.270(a).
(7) ASTM D2382-76, 88, Heat of Combustion of Hydrocarbon Fuels by
Bomb Calorimeter (High-Precision Method), IBR approved June 6, 1984 for
Sec. 61.245(e)(3).
(8) ASTM D2504-67, 77, 88, 93, Noncondensable Gases in
C3 and Lighter Hydrocarbon Products by Gas

[[Page 62151]]

Chromatography, IBR approved June 6, 1984 for Sec. 61.245(e)(3).
(9) ASTM D2986-71, 78, 95a, Standard Method for Evaluation of Air,
Assay Media by the Monodisperse DOP (Dioctyl Phthalate) Smoke Test, IBR
approved for Appendix B: Method 103, Section 6.1.3.
(10) ASTM D4420-94, Standard Test Method for Determination of
Aromatics in Finished Gasoline by Gas Chromatography, IBR approved for
Sec. 61.67(h)(1).
(11) ASTM D4734-87, 96, Standard Specification for Refined Benzene-
545, IBR approved September 14, 1989 for Sec. 61.270(a).
(12) ASTM D4809-95, Standard Test Method for Heat of Combustion of
Liquid Hydrocarbon Fuels by Bomb Calorimeter (Precision Method), IBR
approved for Sec. 61.245(e)(3).
(13) ASTM E50-82, 86, 90 (Reapproved 1995), Standard Practices for
Apparatus Reagents, and Safety Precautions for Chemical Analysis of
Metals, IBR approved for Appendix B: Method 108C, Section 6.1.4.
* * * * *

Sec. 61.20 [Amended]

3. Amend Sec. 61.20 as follows:
a. Paragraph (a) is amended by revising the words ``100,000 tons''
to read ``90,720 megagrams (Mg) (100,000 tons).''
b. Paragraph (b) is amended by revising the words ``10,000 tons''
to read ``9,072 Mg (10,000 tons).''
c. Paragraph (b) is amended by revising the words ``100,000 tons''
to read ``90,720 Mg (100,000 tons).''

61.21 [Amended]

4. In Sec. 61.21(b), the words ``Effective dose equivalent means
the sum of the products of absorbed dose and appropriate factors to
account for differences in biological effectiveness due to the quality
of radiation and its distribution in the body of reference man'' are
revised to read ``Effective dose equivalent means the sum of the
products of the absorbed dose and appropriate effectiveness factors.
These factors account for differences in biological effectiveness due
to the quality of radiation and its distribution in the body of
reference man.''

Sec. 61.23 [Amended]

5. Amend Sec. 61.23 as follows:
a. In paragraph (a), the first sentence is amended by revising the
abbreviation ``EPA'' to read ``U.S. Environmental Protection Agency
(EPA).''
b. In paragraph (a), the second sentence is amended by revising the
word ``Appendix'' to read ``appendix.''

Sec. 61.24 [Amended]

6. Amend Sec. 61.24 as follows:
a. In paragraph (a), the first sentence is amended by revising the
words ``used in making the calculation'' to read ``used in making the
calculations.''
b. In paragraph (a), the second sentence is amended by revising the
words ``Such report shall'' to read ``This report shall.''

Sec. 61.30 [Amended]

7. In Sec. 61.30, paragraph (a) is amended by revising the words
``Extraction plans'' to read ``Extraction plants.''

Sec. 61.32 [Amended]

8. Amend Sec. 61.32 as follows:
a. Paragraph (a) is amended by revising the words ``10 grams'' to
read ``10 grams (0.022 lb).''
b. Paragraphs (b) and (b)(1)(i) are amended by revising the words
``0.01 g/m \3\'' to read ``0.01 g/m \3\
(4.37x10-6 gr/ft \3\)'' wherever they occur.

Sec. 61.42 [Amended]

9. Amend Sec. 61.42 as follows:
a. Paragraph (a) is amended by revising the words ``75 microgram
minutes per cubic meter of air'' to read ``75 microgram minutes per
cubic meter (g-min/m \3\) (4.68 pound minutes per cubic foot
(lb-min/ft \3\)) of air.''
b. Paragraph (b) is amended by revising the words ``2 grams per
hour'' to read ``2.0 g/hr (0.0044 lb/hr).''
c. Paragraph (b) is amended by revising the words ``10 grams per
day'' to read ``10 g/day (0.022 lb/day).''

Sec. 61.52 [Amended]

10. Amend Sec. 61.52 as follows:
a. Paragraph (a) is amended by revising the words ``2300 grams'' to
read ``2.3 kg (5.1 lb).''
b. Paragraph (b) is amended by revising the words ``3200 grams'' to
read ``3.2 kg (7.1 lb).''

Sec. 61.53 [Amended]

11. In Sec. 61.53, paragraph (c) is amended by revising the words
``1,300 gms/day'' to read ``1.3 kg/day (2.9 lb/day).''

Sec. 61.55 [Amended]

12. Amend Sec. 61.55 as follows:
a. In paragraph (a), the second sentence is amended by revising the
words ``1,600 g'' to read ``1.6 kg (3.5 lb).''
b. Paragraph (b)(1) is amended by revising the words ``Reference
Method'' to read ``Method'' wherever they occur.
c. Paragraph (c)(4) is amended by revising the words ``established
in 2'' to read ``established in paragraph (c)(2) of this section.''

Sec. 61.61 [Amended]

13. Amend Sec. 61.61 as follows:
a. Paragraph (c) is amended by revising the words ``polyvinyl
chloride plant'' to read ``polyvinyl chloride (PVC) plant.''
b. In paragraph (l), the first sentence is amended by revising the
words ``a least'' to read ``at least.''
c. Paragraph (w)(3) is amended by revising the words ``Test Method
21'' to read ``Method 21.''

Sec. 61.62 [Amended]

14. In Sec. 61.62, paragraph (b) is amended by revising the words
``0.2 g/kg (0.0002 lb/lb)'' to read ``0.2 g/kg (0.4 lb/ton).''

Sec. 61.64 [Amended]

15. Amend Sec. 61.64 as follows:
a. In paragraph (a)(2), the first sentence is amended by revising
the words ``0.02 g vinyl chloride/kg (0.00002 lb vinyl chloride/lb)''
to read ``0.02 g vinyl chloride/kg (0.04 lb vinyl chloride/ton).''
b. Paragraph (e)(2)(i) is amended by revising the words ``2 g/kg
(0.002 lb/lb)'' to read ``2 g/kg (4 lb/ton).''
c. Paragraph (e)(2)(ii) is amended by revising the words ``0.4 g/kg
(0.0004 lb/lb)'' to read ``0.4 g/kg (0.8 lb/ton).''
d. Paragraph (f)(2)(i) is amended by revising the words ``2.02 g/kg
(0.00202 lb/lb)'' to read ``2.02 g/kg (4.04 lb/ton).''
e. Paragraph (f)(2)(ii) is amended by revising the words ``0.42 g/
kg (0.00042 lb/lb)'' to read ``0.42 g/kg (0.84 lb/ton).''

Sec. 61.65 [Amended]

16. Amend Sec. 61.65 as follows:
a. In paragraph (a), the first sentence is amended by revising the
words ``Relief valve discharge'' to read ``Relief valve discharge
(RVD).''
b. Paragraph (b)(8)(i)(D)(1) is amended by revising the words
``sections 5.2.1. and 5.2.2. of Test Method 106 and in accordance with
section 7.1 of Test Method 106'' to read ``sections 7.2.1 and 7.2.2 of
Method 106 and in accordance with section 10.1 of Method 106.''
c. In paragraph (b)(8)(i)(D)(2), the fourth sentence is amended by
revising the words ``maximum self life'' to read ``maximum shelf
life.''
d. In paragraph (b)(8)(i)(D)(2), the fifth sentence is amended by
revising the words ``section 7.3 of Test Method 106. The requirements
in section 5.2.3.1. and 5.2.3.2. of Test Method 106'' to read
``Sections 8.1 and 9.2 of Method 106. The requirements in Sections
7.2.3.1 and 7.2.3.2 of Method 106.''
e. In paragraph (c), the second sentence is amended by revising the

[[Page 62152]]

words ``Test Method'' to read ``Method 106.''

17. Amend Sec. 61.67 by:
a. Revising Sec. 61.67(g).
b. In paragraph (h)(1) by revising ``ASTM Method D-2267'' to read
``ASTM D2267-68, 78, or 88 or D4420-94.''
The revisions read as follows:

Sec. 61.67 Emission tests.

* * * * *
(g) Unless otherwise specified, the owner or operator shall use the
test methods in Appendix B to this part for each test as required by
paragraphs (g)(1), (g)(2), (g)(3), (g)(4), and (g)(5) of this section,
unless an alternative method has been approved by the Administrator. If
the Administrator finds reasonable grounds to dispute the results
obtained by an alternative method, he may require the use of a
reference method. If the results of the reference and alternative
methods do not agree, the results obtained by the reference method
prevail, and the Administrator may notify the owner or operator that
approval of the method previously considered to be alternative is
withdrawn. Whenever Method 107 is specified, and the conditions in
Section 1.2, ``Applicability'' of Method 107A are met, Method 107A may
be used.
(1) Method 106 is to be used to determine the vinyl chloride
emissions from any source for which an emission limit is prescribed in
Sec. 61.62(a) or (b), Sec. 61.63(a), or Sec. 61.64(a)(1), (b), (c), or
(d), or from any control system to which reactor emissions are required
to be ducted in Sec. 61.64(a)(2) or to which fugitive emissions are
required to be ducted in Sec. 61.65(b)(1)(ii), (b)(2), (b)(5),
(b)(6)(ii), or (b)(9)(ii).
(i) For each run, one sample is to be collected. The sampling site
is to be at least two stack or duct diameters downstream and one half
diameter upstream from any flow disturbance such as a bend, expansion,
contraction, or visible flame. For a rectangular cross section, an
equivalent diameter is to be determined from the following equation:
Equivalent diameter = 2(length)(width)/(length + width)
The sampling point in the duct is to be at the centroid of the
cross section. The sample is to be extracted at a rate proportional to
the gas velocity at the sampling point. The sample is to contain a
minimum volume of 50 liters (1.8 ft3) corrected to standard
conditions and is to be taken over a period as close to 1 hour as
practicable.
(ii) Each emission test is to consist of three runs. For the
purpose of determining emissions, the average of results of all runs is
to apply. The average is to be computed on a time weighted basis.
(iii) For gas streams containing more that 10 percent oxygen, the
concentration of vinyl chloride as determined by Method 106 is to be
corrected to 10 percent oxygen (dry basis) for determination of
emissions by using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.474

Where:

Cb(corrected) = The concentration of vinyl chloride in the
exhaust gases, corrected to 10 percent oxygen.
Cb = The concentration of vinyl chloride as measured by
Method 106.
20.9 = Percent oxygen in the ambient air at standard conditions.
10.9 = Percent oxygen in the ambient air at standard conditions, minus
the 10.0 percent oxygen to which the correction is being made.
Percent O2 = Percent oxygen in the exhaust gas as measured
by Method 3 of Appendix A of Part 60 of this chapter.

(iv) For those emission sources where the emission limit is
prescribed in terms of mass rather than concentration, mass emissions
are to be determined using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.475

Where:

CBX = Vinyl chloride emissions, g/kg (lb/lb) product.
Cb = Concentration of vinyl chloride as measured by Test
Method 106, ppmv.
DVC = Density of vinyl chloride at standard conditions, 2.60
kg/m3 (0.162 lb/ft3).
Q = Volumetric flow rate as determined by Method 2 of Appendix A to
Part 60 of this chapter, m3/hr (ft3/hr).
K = Unit conversion factor, 1,000 g/kg (1 lb/lb).
10-6 = Conversion factor for ppm.
Z = Production rate, kg/hr (lb/hr).

(2) Method 107 or Method 601 (incorporated by reference as
specified in Sec. 61.18) is to be used to determine the concentration
of vinyl chloride in each inprocess wastewater stream for which an
emission limit is prescribed in Sec. 61.65(b)(9)(i).
(3) When a stripping operation is used to attain the emission
limits in Sec. 61.64(e) and (f), emissions are to be determined using
Method 107 as follows:
(i) The number of strippers (or reactors used as strippers) and
samples and the types and grades of resin to be sampled are to be
determined by the Administrator for each individual plant at the time
of the test based on the plant's operation.
(ii) Each sample is to be taken immediately following the stripping
operation.
(iii) The corresponding quantity of material processed by each
stripper (or reactor used as a stripper) is to be determined on a dry
solids basis and by a method submitted to and approved by the
Administrator.
(iv) At the prior request of the Administrator, the owner or
operator shall provide duplicates of the samples required in paragraph
(g)(3)(i) of this section.
(4) Where control technology other than or in addition to a
stripping operation is used to attain the emission limit in
Sec. 61.64(e), emissions are to be determined as follows:
(i) Method 106 is to be used to determine atmospheric emissions
from all of the process equipment simultaneously. The requirements of
paragraph (g)(1) of this section are to be met.
(ii) Method 107 is to be used to determine the concentration of
vinyl chloride in each inprocess wastewater stream subject to the
emission limit prescribed in Sec. 61.64(e). Vinyl chloride mass
emissions are to be determined using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.476

Where:

CBX = Vinyl chloride emissions, g/kg (lb/lb) product in each
inprocess wastewater stream.
Crvc = Concentration of vinyl chloride in wastewater, as
measured by Method 107, ppmw.
Dwater = Density of wastewater, 1.0 kg/m3 (0.0624
lb/ft3).
Qwater = Wastewater flow rate, determined in accordance with
a method which has been submitted to and approved by the Administrator,
m3/hr (ft3/hr).
K = Unit conversion factor, 1,000 g/kg (1 lb/lb).
10-6 = Conversion factor for ppm.
Z = Production rate, kg/hr (lb/hr), determined in accordance with a
method which has been submitted to and approved by the Administrator.

(5) The reactor opening loss for which an emission limit is
prescribed in Sec. 61.64(a)(2) is to be determined. The number of
reactors for which the determination is to be made is to be specified
by the Administrator for each individual plant at the time of the

[[Page 62153]]

determination based on the plant's operation.
(i) Except as provided in paragraph (g)(5)(ii) of this section, the
reactor opening loss is to be determined using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.477

Where:

CBX = Vinyl chloride emissions, g/kg (lb/lb) product.
Cb = Concentration of vinyl chloride, in ppmv, as determined
by Method 106 or a portable hydrocarbon detector which measures
hydrocarbons with a sensitivity of at least 10 ppmv.
VR = Capacity of the reactor, m\3\ (ft\3\).
DVC = Density of vinyl chloride at standard conditions, 2.60
kg/m\3\ (0.162 lb/ft\3\).
K = Unit conversion factor, 1,000 g/kg (1 lb/lb).
10-\6\ = Conversion factor for ppm.
Z = Production rate, kg/hr (lb/hr).

(A) If Method 106 is used to determine the concentration of vinyl
chloride (Cb), the sample is to be withdrawn at a constant
rate with a probe of sufficient length to reach the vessel bottom from
the manhole. Samples are to be taken for 5 minutes within 6 inches of
the vessel bottom, 5 minutes near the vessel center, and 5 minutes near
the vessel top.
(B) If a portable hydrocarbon detector is used to determine the
concentration of vinyl chloride (Cb), a probe of sufficient
length to reach the vessel bottom from the manhole is to be used to
make the measurements. One measurement will be made within 6 inches of
the vessel bottom, one near the vessel center and one near the vessel
top. Measurements are to be made at each location until the reading is
stabilized. All hydrocarbons measured are to be assumed to be vinyl
chloride.
(C) The production rate of polyvinyl chloride (Z), which is the
product of the average batch weight and the number of batches produced
since the reactor was last opened to the atmosphere, is to be
determined by a method submitted to and approved by the Administrator.
(ii) A calculation based on the number of evacuations, the vacuum
involved, and the volume of gas in the reactor is hereby approved by
the Administrator as an alternative method for determining reactor
opening loss for postpolymerization reactors in the manufacture of bulk
resins. Calculation methods based on techniques other than repeated
evacuation of the reactor may be approved by the Administrator for
determining reactor opening loss for postpolymerization reactors in the
manufacture of bulk resins.
(6) For a reactor that is used as a stripper, the emissions of
vinyl chloride from reactor opening loss and all sources following the
reactor used as a stripper for which an emission limit is prescribed in
Sec. 61.64(f) are to be determined. The number of reactors for which
the determination is to be made is to be specified by the Administrator
for each individual plant at the time of the determination based on the
plant's operation.
(i) For each batch stripped in the reactor, the following
measurements are to be made:
(A) The concentration of vinyl chloride in resin after stripping,
measured according to paragraph (g)(3) of this section;
(B) The reactor vacuum at end of strip from plant instrument; and
(C) The reactor temperature at the end of strip from plant
instrument.
(ii) For each batch stripped in the reactor, the following
information is to be determined:
(A) The vapor pressure of water in the reactor at the end of strip
from the following table:

Metric Units
----------------------------------------------------------------------------------------------------------------
Reactor vapor Reactor vapor Reactor vapor H2O vapor
temperature ( H2O vapor temperature ( H2O vapor pressure temperature ( pressure (mm
deg.C) pressure (mm Hg) deg.C) (mm Hg) deg.C) Hg)
----------------------------------------------------------------------------------------------------------------
40 55.3 62 163.8 84 416.8
41 58.3 63 171.4 85 433.6
42 61.5 64 179.3 86 450.9
43 64.8 65 187.5 87 468.7
44 68.3 66 196.1 88 487.1
45 71.9 67 205.0 89 506.1
46 75.6 68 214.2 90 525.8
47 79.6 69 223.7 91 546.0
48 83.7 70 233.7 92 567.0
49 88.0 71 243.9 93 588.6
50 92.5 72 254.6 94 610.9
51 97.2 73 265.7 95 633.9
52 102.1 74 277.2 96 657.6
53 107.2 75 289.1 97 682.1
54 112.5 76 301.4 98 707.3
55 118.0 77 314.1 99 733.2
56 123.8 78 327.3 100 760.0
57 129.8 79 341.0
58 136.1 80 355.1
59 142.6 81 369.7
60 149.4 82 384.9
61 156.4 83 400.6
----------------------------------------------------------------------------------------------------------------

[[Page 62154]]

English Units
----------------------------------------------------------------------------------------------------------------
Reactor vapor H2O vapor Reactor vapor Reactor vapor
temperature ( pressure temperature ( H2O vapor pressure temperature ( H2O vapor
deg.F) (psia) deg.F) (psia) deg.F) pressure (psia)
----------------------------------------------------------------------------------------------------------------
104 1.07 144 3.167 183 8.060
106 1.13 145 3.314 185 8.384
108 1.19 147 3.467 187 8.719
109 1.25 149 3.626 189 9.063
111 1.32 151 3.792 190 9.419
113 1.39 153 3.964 192 9.786
115 1.46 154 4.142 194 10.17
117 1.54 156 4.326 196 10.56
118 1.62 158 4.519 198 10.96
120 1.70 160 4.716 199 11.38
122 1.79 162 4.923 201 11.81
124 1.88 163 5.138 203 12.26
126 1.974 165 5.360 205 12.72
127 2.073 167 5.590 207 13.19
129 2.175 169 5.828 208 13.68
131 2.282 170 6.074 210 14.18
133 2.394 172 6.329 212 14.70
135 2.510 174 6.594
136 2.632 176 6.866
138 2.757 178 7.149
140 2.889 180 7.443
142 3.024 181 7.746
----------------------------------------------------------------------------------------------------------------

(B) The partial pressure of vinyl chloride in reactor at end of
strip from the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.478

Where:

PPVC = Partial pressure of vinyl chloride, mm Hg (psia)
PATM = Atmospheric pressure at 0 deg.C (32 deg.F), 760 mm
Hg (14.7 psia)
PRV = Absolute pressure of reactor vacuum, mm Hg (psia)
PW = Vapor pressure of water, mm Hg (psia)

(C) The reactor vapor space volume at the end of the strip from the
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.479

Where:

VRVS = Reactor vapor space volume, m\3\ (ft\3\)
VR = Reactor capacity, m\3\ (ft\3\)
VW = Volume of water in reactor from recipe, m\3\ (ft\3\)
WPVC = Dry weight of polyvinyl chloride in reactor from
recipe, kg (lb)
DPVC = Typical density of polyvinyl chloride, 1,400 kg/m\3\
(87.4 lb/ft\3\)

(iii) For each batch stripped in the reactor, the combined reactor
opening loss and emissions from all sources following the reactor used
as a stripper is to be determined using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.480

Where:

CBX = Vinyl chloride emissions, g/kg (lb/lb) product.
PPMVC = Concentration of vinyl chloride in resin after
stripping, ppmw
K1 = Conversion factor from ppmw to units of emission
standard, 0.001 (metric units) = 0.002 (English units)
PPVC = Partial pressure of vinyl chloride determined
according to paragraph (g)(6)(ii)(B) of this section, mm Hg (psia)
VRVS = Reactor vapor space volume determined according to
paragraph (g)(6)(ii)(C) of this section, m\3\ (ft\3\)
RVC = Ideal gas constant for vinyl chloride, 1,002 g- deg.K/
(mm Hg-m\3\) [5.825 lb- deg.R/(psia-ft\3\)]
MPVC = Dry weight of polyvinyl chloride in reactor from
recipe, kg (lb)
TR = Reactor temperature, deg.C ( deg.F)
KT = Temperature conversion factor for deg.C to deg.K, 273
( deg.F to deg.R, 460)

(h)(1) Each piece of equipment within a process unit that can
reasonably contain equipment in vinyl chloride service is presumed to
be in vinyl chloride service unless an owner or operator demonstrates
that the piece of equipment is not in vinyl chloride service. For a
piece of equipment to be considered not in vinyl chloride service, it
must be determined that the percent vinyl chloride content can be
reasonably expected not to exceed 10 percent by weight for liquid
streams or contained liquid volumes and 10 percent by volume for gas
streams or contained gas volumes, which also includes gas volumes above
liquid streams or contained liquid volumes. For purposes of determining
the percent vinyl chloride content of the process fluid that is
contained in or contacts equipment, procedures that conform to the
methods described in ASTM Method D-2267 (incorporated by

[[Page 62155]]

reference as specified in Sec. 61.18) shall be used.
(2)(i) An owner or operator may use engineering judgment rather
than the procedures in paragraph (h)(1) of this section to demonstrate
that the percent vinyl chloride content does not exceed 10 percent by
weight for liquid streams and 10 percent by volume for gas streams,
provided that the engineering judgment demonstrates that the vinyl
chloride content clearly does not exceed 10 percent. When an owner or
operator and the Administrator do not agree on whether a piece of
equipment is not in vinyl chloride service, however, the procedures in
paragraph (h)(1) of this section shall be used to resolve the
disagreement.
(ii) If an owner or operator determines that a piece of equipment
is in vinyl chloride service, the determination can be revised only
after following the procedures in paragraph (h)(1) of this section.
(3) Samples used in determining the percent vinyl chloride content
shall be representative of the process fluid that is contained in or
contacts the equipment.

Sec. 61.68 [Amended]

18. Amend Sec. 61.68 as follows:
a. Paragraph (c)(1) is amended by revising the words ``sections
5.2.1. and 5.2.2. of Test Method 106 and in accordance with section 7.1
of Test Method 106'' to read ``Sections 7.2.1 and 7.2.2 of Method 106
and in accordance with Section 10.1 of Method 106.''
b. In paragraph (c)(2), the fifth sentence is amended by revising
the words ``section 7.3 of Test Method 106. The requirements in section
5.2.3.1. and 5.2.3.2. of Test Method 106'' to read ``Sections 8.1 and
9.2 of Method 106. The requirements in Sections 7.2.3.1 and 7.2.3.2 of
Method 106.''

19. Sec. 61.70(c) is revised as follows: 18440

Sec. 61.70 Reporting.

* * * * *
(c) Unless otherwise specified, the owner or operator shall use the
test methods in Appendix B to this part to conduct emission tests as
required by paragraphs (c)(2) and (c)(3) of this section, unless an
alternative method has been approved by the Administrator. If the
Administrator finds reasonable grounds to dispute the results obtained
by an alternative method, he may require the use of a reference method.
If the results of the reference and alternative methods do not agree,
the results obtained by the reference method prevail, and the
Administrator may notify the owner or operator that approval of the
method previously considered to be alternative is withdrawn.
(1) The owner or operator shall include in the report a record of
the vinyl chloride content of emissions for each 3-hour period during
which average emissions are in excess of the emission limits in
Sec. 61.62(a) or (b), Sec. 61.63(a), or Sec. 61.64(a)(1), (b), (c), or
(d), or during which average emissions are in excess of the emission
limits specified for any control system to which reactor emissions are
required to be ducted in Sec. 61.64(a)(2) or to which fugitive
emissions are required to be ducted in Sec. 61.65(b)(I)(ii), (b)(2),
(b)(5), (b)(6)(ii), or (b)(9)(ii). The number of 3-hour periods for
which average emissions were determined during the reporting period
shall be reported. If emissions in excess of the emission limits are
not detected, the report shall contain a statement that no excess
emissions have been detected. The emissions are to be determined in
accordance with Sec. 61.68(e).
(2) In polyvinyl chloride plants for which a stripping operation is
used to attain the emission level prescribed in Sec. 61.64(e), the
owner or operator shall include in the report a record of the vinyl
chloride content in the polyvinyl chloride resin.
(i) If batch stripping is used, one representative sample of
polyvinyl chloride resin is to be taken from each batch of each grade
of resin immediately following the completion of the stripping
operation, and identified by resin type and grade and the date and time
the batch is completed. The corresponding quantity of material
processed in each stripper batch is to be recorded and identified by
resin type and grade and the date and time the batch is completed.
(ii) If continuous stripping is used, one representative sample of
polyvinyl chloride resin is to be taken for each grade of resin
processed or at intervals of 8 hours for each grade of resin which is
being processed, whichever is more frequent. The sample is to be taken
as the resin flows out of the stripper and identified by resin type and
grade and the date and time the sample was taken. The corresponding
quantity of material processed by each stripper over the time period
represented by the sample during the 8-hour period, is to be recorded
and identified by resin type and grade and the date and time it
represents.
(iii) The vinyl chloride content in each sample is to be determined
by Method 107 as prescribed in Sec. 61.67(g)(3).
(iv) [Reserved]
(v) The report to the Administrator by the owner or operator is to
include a record of any 24-hour average resin vinyl chloride
concentration, as determined in this paragraph, in excess of the limits
prescribed in Sec. 61.64(e). The vinyl chloride content found in each
sample required by paragraphs (c)(2)(i) and (c)(2)(ii) of this section
shall be averaged separately for each type of resin, over each calendar
day and weighted according to the quantity of each grade of resin
processed by the stripper(s) that calendar day, according to the
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.481

Where:

AT = 24-hour average concentration of type T resin in ppm
(dry weight basis).
QT = Total production of type T resin over the 24-hour
period, in kg (ton).
T = Type of resin.
MGi = Concentration of vinyl chloride in one sample of grade
Gi resin in ppm.
PGi = Production of grade Gi resin represented by
the sample, in kg (ton).
Gi = Grade of resin: e.g., G1, G2,
G3.
n = Total number of grades of resin produced during the 24-hour period.

The number of 24-hour average concentrations for each resin type
determined during the reporting period shall be reported. If no 24-hour
average resin vinyl chloride concentrations in excess of the limits
prescribed in

[[Page 62156]]

Sec. 61.64(e) are measured, the report shall state that no excess resin
vinyl chloride concentrations were measured.
(vi) The owner or operator shall retain at the source and make
available for inspection by the Administrator for a minimum of 3 years
records of all data needed to furnish the information required by
paragraph (c)(2)(v) of this section. The records are to contain the
following information:
(A) The vinyl chloride content found in all the samples required in
paragraphs (c)(2)(i) and (c)(2)(ii) of this section, identified by the
resin type and grade and the time and date of the sample, and
(B) The corresponding quantity of polyvinyl chloride resin
processed by the stripper(s), identified by the resin type and grade
and the time and date it represents.
(3) The owner or operator shall include in the report a record of
any emissions from each reactor opening in excess of the emission
limits prescribed in Sec. 61.64(a)(2). Emissions are to be determined
in accordance with Sec. 61.67(g)(5), except that emissions for each
reactor are to be determined. The number of reactor openings during the
reporting period shall be reported. If emissions in excess of the
emission limits are not detected, the report shall include a statement
that excess emissions have not been detected.
(4) In polyvinyl chloride plants for which stripping in the reactor
is used to attain the emission level prescribed in Sec. 61.64(f), the
owner or operator shall include in the report a record of the vinyl
chloride emissions from reactor opening loss and all sources following
the reactor used as a stripper.
(i) One representative sample of polyvinyl chloride resin is to be
taken from each batch of each grade of resin immediately following the
completion of the stripping operation, and identified by resin type and
grade and the date and time the batch is completed. The corresponding
quantity of material processed in each stripper batch is to be recorded
and identified by resin type and grade and the date and time the batch
is completed.
(ii) The vinyl chloride content in each sample is to be determined
by Method 107 as prescribed in Sec. 61.67(g)(3).
(iii) The combined emissions from reactor opening loss and all
sources following the reactor used as a stripper are to be determined
for each batch stripped in a reactor according to the procedure
prescribed in Sec. 61.67(g)(6).
(iv) The report to the Administrator by the owner or operator is to
include a record of any 24-hour average combined reactor opening loss
and emissions from all sources following the reactor used as a stripper
as determined in this paragraph, in excess of the limits prescribed in
Sec. 61.64(f). The combined reactor opening loss and emissions from all
sources following the reactor used as a stripper associated with each
batch are to be averaged separately for each type of resin, over each
calendar day and weighted according to the quantity of each grade of
resin stripped in reactors that calendar day as follows:
For each type of resin (suspension, dispersion, latex, bulk,
other), the following calculation is to be performed:
[GRAPHIC] [TIFF OMITTED] TR17OC00.482

Where:

AT = 24-hour average combined reactor opening loss and
emissions from all sources following the reactor used as a stripper, in
g vinyl chloride/kg (lb/ton) product (dry weight basis).
QT = Total production of resin in batches for which
stripping is completed during the 24-hour period, in kg (ton).
T = Type of resin.
CGi = Average combined reactor opening loss and emissions
from all sources following the reactor used as a stripper of all
batches of grade Gi resin for which stripping is completed
during the 24-hour period, in g vinyl chloride/kg (lb/ton) product (dry
weight basis) (determined according to procedure prescribed in
Sec. 61.67(g)(6)).
PGi = Production of grade Gi resin in the batches
for which C is determined, in kg (ton).
Gi = Grade of resin: e.g., G1, G2,
G3.
n = Total number of grades of resin in batches for which stripping is
completed during the 24-hour period.

The number of 24-hour average emissions determined during the
reporting period shall be reported. If no 24-hour average combined
reactor opening loss and emissions from all sources following the
reactor used as a stripper in excess of the limits prescribed in
Sec. 61.64(f) are determined, the report shall state that no excess
vinyl chloride emissions were determined.
* * * * *

Sec. 61.93 [Amended]

20. In Sec. 61.93, paragraphs (b)(1)(I), (b)(1)(ii), and (b)(2)(I)
are amended by revising the words ``Reference Method'' to read
``Method'' wherever they occur.

Sec. 61.107 [Amended]

21. Amend Sec. 61.107 as follows:
a. Paragraphs (b)(1)(I), (b)(1)(ii), and (b)(2)(I) are amended by
revising the words ``Reference Method'' to read ``Method'' wherever
they occur.
b. Paragraphs (b)(2)(iv) and (b)(5)(v) are amended by revising the
words ``method 114'' to read ``Method 114'' wherever they occur.
c. Paragraph (b)(5)(iv) is amended by revising the words ``table
2'' to read ``Table 2'', wherever they occur.

Sec. 61.110 [Amended]

22. In Sec. 61.110, paragraph (c)(2) is amended by revising the
words ``1,000 megagrams'' to read ``1,000 megagrams (1,102 tons).''

Sec. 61.123 [Amended]

23. Amend Sec. 61.123 as follows:
a. Paragraph (d) is amended by revising the words ``curies per
metric ton'' to read ``curies per Mg or curies per ton'' wherever they
occur.
b. In paragraph (d), the fifth sentence is amended by revising the
words ``in metric tons'' to read ``in Mg (tons).''

Sec. 61.125 [Amended]

24. Amend Sec. 61.125 as follows:
a. Paragraph (a)(1) is amended by revising the words ``Test Method
1 of Appendix A'' to read ``Method 1 of Appendix A.''
b. Paragraph (a)(2) is amended by revising the words ``Test Method
2 of Appendix A'' to read ``Method 2 of Appendix A.''
c. Paragraph (a)(3) is amended by revising the words ``Test Method
3 of Appendix A'' to read ``Method 3 of Appendix A.''
d. Paragraph (a)(4) is amended by revising the words ``Test Method
5 of

[[Page 62157]]

Appendix A'' to read ``Method 5 of Appendix A.''
e. Paragraph (a)(5) is amended by revising the words ``Test Method
111 of Appendix B'' to read ``Method 111 of Appendix B.''

Sec. 61.132 [Amended]

25. In Sec. 61.132, paragraphs (b) and (b)(1) are amended by
revising the words ``Reference Method'' to read ``Method'' wherever
they occur.

Sec. 61.133 [Amended]

26. In Sec. 61.133, paragraphs (c) and (c)(1) are amended by
revising the words ``Reference Method'' to read ``Method'' wherever
they occur.

27. Amend Sec. 61.139 as follows:
a. In paragraph (c)(1), the equation definitions for
``Qaj'' and ``Qbi'' are revised.
b. Paragraph (d)(2)(ii) is amended by revising the words ``method
21'' to read ``Method 21'' wherever they occur.
c. In paragraph (g)(1)(vi), the second sentence is amended by
revising the words ``Either follow section 7.1, ``Integrated Bag
Sampling and Analysis,'' or section 7.2, ``Direct Interface Sampling
and Analysis Procedure'''' to read ``Either the integrated bag sampling
and analysis procedure or the direct interface procedure may be used.''
d. Paragraph (g)(1)(vi)(A) is amended by revising the words
``section 7.1'' to read ``the integrated bag sampling and analysis
procedure.''
e. In paragraph (g)(1)(vi)(B), the first sentence is amended by
revising the words ``section 7.2'' to read ``the direct interface
sampling and analysis procedure.''
f. Paragraphs (h)(3), (h)(3)(ii), and (h)(4)(ii) are amended by
revising the words ``method 18'' to read ``Method 18'' wherever they
occur.
The revisions read as follows:

Sec. 61.139 Provisions for alternative means for process vessels,
storage tanks, and tar-intercepting sumps.

* * * * *
(c) * * *
(1) * * *

Qaj = volumetric flow rate in vents after the control
device, standard cubic meters/minute (scm/min) [standard cubic feet/
minute (scf/min)].
Qbi = volumetric flow rate in vents before the control
device, scm/min (scf/min).
* * * * *

61.155 [Amended]

28. In Sec. 61.155, the section heading is amended by revising the
words ``asbesto-containing'' to read ``asbestos-containing.''

Sec. 61.162 [Amended]

29. Amend Sec. 61.162 as follows:
a. Paragraph (a)(1) is amended by revising the words ``2.5 Mg per
year'' to read ``2.5 Mg (2.7 ton) per year.''
b. Paragraph (b)(1) is amended by revising the words ``0.4 Mg per
year'' to read ``0.4 Mg (0.44 ton) per year.''

30. Amend Sec. 61.164 as follows:
a. Paragraph (c) is amended by revising the words ``8.0 Mg per
year'' to read ``8.0 Mg (8.8 ton) per year.''
b. Paragraph (c) is amended by revising the words ``1.0 Mg per
year'' to read ``1.0 Mg (1.1 ton) per year.''
c. In paragraph (c)(1), the first sentence is amended by revising
the words ``grams of elemental arsenic per kilogram'' to read ``grams
of elemental arsenic per kilogram (pounds per ton).''
d. Paragraphs (c)(1) and (d)(3) are revised; the equation and
definitions in paragraphs (c)(2) and (d)(5) are revised; and the
definitions of the terms ``Ra'' and ``Ti'' in
paragraph (d)(4) are revised.
e. Paragraph (d) is amended by revising the words ``8.0 Mg per
year'' to read ``8.0 Mg (8.8 ton) per year.''
f. Paragraph (d) is amended by revising the words ``1.0 Mg per
year'' to read ``1.0 Mg (1.1 ton) per year.''
g. Paragraph (d)(2)(i) is amended by revising the words ``emission
rate (g/h)'' to read ``emission rate, g/hr (lb/hr).''
h. Paragraph (d)(2)(ii)(D) is amended by revising the words
``Section 4 of Method 5D'' to read ``Section 8.0 of Method 5D.''
i. Paragraph (e)(1)(ii)(D) is amended by revising the words
``Section 4 of Method 5D'' to read ``Section 8.0 of Method 5D.''
The revisions read as follows:

Sec. 61.164 Test methods and procedures.

* * * * *
(c) * * *
(1) Derive a theoretical uncontrolled arsenic emission factor (T),
based on material balance calculations for each arsenic-containing
glass type (i) produced during the 12-month period, as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.483

Where:

Ti = The theoretical uncontrolled arsenic emission factor
for each glass type (i), g/kg (lb/ton).
Abi = Fraction by weight of elemental arsenic in the fresh
batch for each glass type (I).
Wbi = Weight of fresh batch melted per unit weight of glass
produced for each glass type (i), g/kg (lb/ton).
Aci = Fraction by weight of elemental arsenic in cullet for
each glass type (i).
Wci = Weight of cullet melted per unit weight of glass
produced for each glass type (i), g/kg (lb/ton).
Bgi = Weight of elemental arsenic per unit weight of glass
produced for each glass type (i), g/kg (lb/ton).

(2) * * *
[GRAPHIC] [TIFF OMITTED] TR17OC00.484

Where:

Yi = Theoretical uncontrolled arsenic emission estimate for
the 12-month period for each glass type, Mg/year (ton/year).
Ti = Theoretical uncontrolled arsenic emission factor for
each type of glass (i) produced during the 12-month period as
calculated in paragraph (c)(1) of this section, g/kg (lb/ton).
Gi = Quantity of each arsenic-containing glass type (i)
produced during the 12-month period, kg/yr (ton/yr).
K = conversion factor for unit consistency, 106 g/Mg (2,000
lb/ton).
* * * * *
(d) * * *
(3) Determine the actual uncontrolled arsenic emission factor
(Ra) as follows:

[[Page 62158]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.485

Where:

Ra = Actual uncontrolled arsenic emission factor, g/kg (lb/
ton).
Ea = Actual uncontrolled arsenic emission rate from
paragraph (d)(2) of this section, g/hr (lb/hr).
P = Rate of glass production, kg/hr (ton/hr), determined by dividing
the weight of glass pulled from the furnace during the emission test by
the number of hours taken to perform the test under paragraph (d)(2) of
this section.

(4) * * *

Ra = Actual uncontrolled arsenic emission factor, determined
in paragraph (d)(3) of this section, g/kg (lb/ton).
Ti = Theoretical uncontrolled arsenic emission factor, g/kg
(lb/ton), determined in paragraph (c)(1) of this section for the same
glass type for which Ra was determined.

(5) * * *
[GRAPHIC] [TIFF OMITTED] TR17OC00.486

Where:

U = Uncontrolled arsenic emission rate for the 12-month period, Mg/yr
(ton/yr).
Ti = Theoretical uncontrolled arsenic emission factor for
each type of glass (i) produced during the 12-month period as
calculated in paragraph (c)(1) of this section, g/kg (lb/ton).
F = The correction factor calculated in paragraph (d)(4) of this
section.
Gi = Quantity of each arsenic-containing glass type (i)
produced during the 12-month period, kg/yr (ton/yr).
n = Number of arsenic-containing glass types produced during the 12-
month period.
K = Conversion factor for unit consistency, 10\6\ g/Mg (2,000 lb/ton).
* * * * *

Sec. 61.165 [Amended]

31. In Sec. 61.165, paragraph (a)(7) is amended by revising the
words ``all records of maintenance'' at the beginning of the sentence
to read ``All maintenance.''

Sec. 61.172 [Amended]

32. Amend Sec. 61.172 as follows:
a. Paragraph (a) is amended by revising the words ``75 kg/h'' to
read ``75 kg/hr (165 lb/hr).''
b. Paragraph (c) is amended by revising the words ``11.6 milligrams
per dry standard cubic meter'' to read ``11.6 mg/dscm (0.0051 gr/
dscf).''

Sec. 61.174 [Amended]

33. In Sec. 61.174, paragraph (f)(3)is amended by revising the
equation definitions as follows:

Sec. 61.174 Test methods and procedures.

* * * * *
(f) * * *
(3) * * *

Rc is the converter arsenic charging rate, kg/hr (lb/hr).
Ac is the monthly average weight percent of arsenic in the
copper matte charged during the month(%) as determined under paragraph
(f)(2) of this section.
Al is the monthly average weight percent of arsenic in the
lead matte charged during the month(%) as determined under paragraph
(f)(2) of this section.
Wci is the total rate of copper matte charged to a copper
converter during the month, kg (lb).
Wli is the total rate of lead matte charged to a copper
converter during the month, kg (lb).
Hc is the total number of hours the copper converter
department was in operation during the month (hr).
n is the number of copper converters in operation during the month.
* * * * *

Sec. 61.192 [Amended]

34. In Sec. 61.192, the first sentence is amended by revising the
words ``20 pCi/-m\2\-s'' to read ``20 picocuries per square meter per
second (pCi/(m\2\-sec)) (1.9 pCi/(ft\2\-sec)).''

Sec. 61.202 [Amended]

35. In Sec. 61.202, the third sentence is amended by revising the
words ``20 pCi/m\2\-s'' to read ``20 pCi/(m\2\-sec) (1.9 pCi/(ft\2\-
sec)).''

Sec. 61.204 [Amended]

36. In Sec. 61.204, paragraph (b) is amended by revising the words
``10 picocuries per gram (pCi/g)'' to read ``10 pCi/g (4500 pCi/lb).''

Sec. 61.205 [Amended]

37-38. In Sec. 61.205, paragraph (b)(2) is amended by revising the
words ``7,000 pounds'' to read ``3182 kg (7,000 lb)'' wherever they
occur.

Sec. 61.208 [Amended]

39. Amend Sec. 61.208 as follows:
a. Paragraph (a)(1)(iii) is amended by revising the words
``quantity (in pounds) of phosphogypsum'' are revised to read
``quantity of phosphogypsum, in kilograms or pounds.''
b. Paragraph (a)(1)(vi) is amended by revising the words ``in pCi/
g'' to read ``in pCi/g (pCi/lb).''

Sec. 61.222 [Amended]

40. In Sec. 61.222, paragraph (a) is amended by revising the words
``20 pCi/m\2\-s'' to read ``20 pCi/(m\2\-sec) (1.9 pCi/(ft\2\-sec)).''

Sec. 61.241 [Amended]

41. In Sec. 61.241, the definition of the term ``In vacuum
service'' is amended by revising the words ``5 kilopascals (kPa)
below'' to read ``5 kilopascals (kPa) (0.7 psia) below.''

Sec. 61.242-11 [Amended]

42. In Sec. 61.242-11, paragraph (c) is amended by revising the
words ``760 deg.C'' to read ``760 deg.C (1,400 deg.F).''

Sec. 61.243-2 [Amended]

43. Amend Sec. 61.243-2 as follows:
a. Paragraph (b)(2) is amended by revising the words ``skip 1 of
the'' to read ``skip one of the.''
b. Paragraph (b)(3) is amended by revising the words ``After 5
consecutive'' to read ``After five consecutive.''
c. Paragraph (b)(3) is amended by revising the words ``skip 3 of
the quartely'' to read ``skip three of the quarterly.''

Sec. 61.244 [Amended]

44. Amend Sec. 61.244 as follows:
a. In paragraph (b)(1) by revising the words ``emission
limitation.limitation to test data'' to read ``emission limitation to
test data.''
b. By redesignating paragraph (b)(3) as paragraph (b)(2).

Sec. 61.245 [Amended]

45-46. Amend Sec. 61.245 as follows:
a. Paragraphs (b)(2), (b)(3), (b)(5), (c)(2), (c)(3), (e)(3), and
(e)(4) are amended by revising the words ``Reference Method'' to read
``Method'' wherever they occur.
b. In paragraph (e)(3), the definitions of the terms
``HT'', ``K'', ``Ci'', and ``Hi'' are
revised; and the equation and definitions in (e)(5) are revised as
follows:

[[Page 62159]]

Sec. 61.245 Test methods and procedures.

* * * * *
(e) * * *
(3) * * *
HT = Net heating value of the sample, MJ/scm (BTU/scf);
where the net enthalpy per mole of offgas is based on combustion at 25
deg.C and 760 mm Hg (77 deg.F and 14.7 psi), but the standard
temperature for determining the volume corresponding to one mole is 20
deg.C (68 deg.F).
K = conversion constant, 1.740 x 10 \7\ (g-mole) (MJ)/(ppm-scm-kcal)
(metric units); or 4.674 x 10\8\ ((g-mole) (Btu)/(ppm-scf-kcal))
(English units)
Ci = Concentration of sample component ``i'' in ppm, as measured by
Method 18 of Appendix A to 40 CFR Part 60 and ASTM D2504-67, 77, or 88
(Reapproved 1993) (incorporated by reference as specified in
Sec. 61.18).
Hi = net heat of combustion of sample component ``i'' at 25
deg.C and 760 mm Hg (77 deg.F and 14.7 psi), kcal/g-mole. The heats of
combustion may be determined using ASTM D2382-76 or 88 or D4809-95
(incorporated by reference as specified in Sec. 61.18) if published
values are not available or cannot be calculated.
* * * * *
(5) * * *
[GRAPHIC] [TIFF OMITTED] TR17OC00.487

Where:

Vmax = Maximum permitted velocity, m/sec (ft/sec).
HT = Net heating value of the gas being combusted, as
determined in paragraph (e)(3) of this section, MJ/scm (Btu/scf).
K1 = 8.706 m/sec (metric units)
= 28.56 ft/sec (English units)
K2 = 0.7084 m4/(MJ-sec) (metric units)
= 0.087 ft4/(Btu-sec) (English units)
* * * * *

Sec. 61.252 [Amended]

47. In Sec. 61.252, paragraph (a) is amended by revising the words
``20 pCi/m2-s'' to read 20 pCi/(m2-sec) (1.9 pCi/
(ft2-sec)).

Sec. 61.270 [Amended]

48. Amend Sec. 61.270 as follows:
a. Paragraph (a) is revised.
b. Paragraph (e) is amended by revising the words ``204.9 kPa'' to
read ``204.9 kPa (29.72 psia).''
The revisions read as follows:

Sec. 61.270 Applicability and designation of sources.

(a) The source to which this subpart applies is each storage vessel
that is storing benzene having a specific gravity within the range of
specific gravities specified in ASTM D836-84 for Industrial Grade
Benzene, ASTM D835-85 for Refined Benzene-485, ASTM D2359-85a or 93 for
Refined Benzene-535, and ASTM D4734-87 or 96 for Refined Benzene-545.
These specifications are incorporated by reference as specified in
Sec. 61.18. See Sec. 61.18 for acceptable versions of these methods.
* * * * *

Sec. 61.272 [Amended]

49. Amend Sec. 61.272 as follows:
a. In paragraph (c)(1)(i), the fourth sentence is amended by
revising the words ``816 deg.C'' to read ``816 deg.C (1,500
deg.F).''
b. Paragraph (d) is amended by revising the letter ``O'' in the
words ``40 CFR 6O.18(e)'' to read ``40 CFR 60.18(e).''

Sec. 61.301 [Amended]

50. Amend Sec. 61.301 as follows:
a. The definitions of the terms ``Leak'' and ``Vapor-tight marine
vessel'' are amended by revising the words ``method 21'' to read
``Method 21'' wherever they occur.
b. In the definition of the terms ``Vapor-tight tank truck or
vapor-tight railcar'', the second sentence is amended by revising the
words ``method 27 of part 60, appendix A'' to read ``Method 27 of
Appendix A to 40 CFR part 60.''

Sec. 61.302 [Amended]

51. Amend Sec. 61.302 as follows:
a. In paragraph (d)(1), the third sentence is amended by revising
the words ``method 27 of part 60, appendix A'' to read ``Method 27 of
Appendix A to 40 CFR Part 60.''
b. In paragraph (e)(2), the second sentence is amended by revising
the words ``method 21 of part 60, appendix A'' to read ``Method 21 of
Appendix A to 40 CFR Part 60.''
c. In paragraph (e)(2)(ii)(B), fourth sentence, the words ``method
21'' are revised to read ``Method 21 of Appendix A to 40 CFR Part 60.''
d. In paragraph (h), the first sentence is amended by revising the
words ``method 27 of part 60, appendix A'' to read ``Method 27 of
Appendix A to 40 CFR Part 60.''

Sec. 61.303 [Amended]

52. In Sec. 61.303, paragraphs (c), (c)(1), and (c)(2) are amended
by revising the words ``44 MW'' to read ``44 MW (150 x 106
BTU/hr)'' wherever they occur.

Sec. 61.304 [Amended]

53. Amend Sec. 61.304 as follows:
a. Paragraph (a)(4)(iii) is amended by revising the word ``method''
to read ``Method.''
b. In paragraph (a)(4)(iv), the first sentence is amended by
revising the words ``method 25A or method 25B'' to read ``Method 25A or
Method 25B.''
c. Paragraph (b) is amended by revising the words ``a performance
test according to method 22 of appendix A of this part, shall be
performed to determine visible emissions. The observation period shall
be at least 2 hours and shall be conducted according to method 22'' to
read ``a performance test according to Method 22 of appendix A of 40
CFR part 60 shall be performed to determine visible emissions. The
observation period shall be at least 2 hours.''

54. Amend Sec. 61.305 as follows:
a. Paragraphs (a), (b)(3), and (d) are amended by revising the
words ``44 MW'' to read ``44 MW (150 x 106 BTU/hr)''
wherever they occur.
b. Paragraph (a)(3)(ii) is revised.
c. Paragraphs (b)(1), (b)(2), and (b)(3) are amended by revising
the words ``28 deg.C'' to read ``28 deg.C (50 deg.F)'' wherever they
occur.
The revisions read as follows:

Sec. 61.305 Reporting and recordkeeping.

(a) * * *
(3) * * *
(ii) The average combustion temperature of the steam generating
unit or process heater with a design heat input capacity of less than
44 MW (150 x 106 BTU/hr), measured with the following
frequency: at least every 2 minutes during a loading cycle if the total
time period of the loading cycle is less than 3 hours, and every 15
minutes if the total time period of the loading cycle is equal to or
greater than 3 hours. The measured temperature shall be averaged over
the loading cycle.
* * * * *

Sec. 61.342 [Amended]

55. Amend Sec. 61.342 as follows:
a. In paragraph (a), the first sentence, the words ``10 megagrams
per year (Mg/yr)'' are revised to read ``10 megagrams per year (Mg/yr)
(11 ton/yr).''
b. Paragraphs (a)(3), (b), (c), (c)(3)(i), (d), and (e) are amended
by revising the words ``10 Mg/yr'' to read ``10 Mg/yr (11 ton/yr).''
c. Paragraph (c)(3)(i) is amended by revising the words ``0.02
liters per minute'' to read ``0.02 liters per minute (0.005 gallons per
minute).''
d. Paragraph (c)(3)(ii)(B) is amended by revising the words ``2.0
Mg/yr'' to read ``2.0 Mg/yr (2.2 ton/yr).''

[[Page 62160]]

e. Paragraph (d)(2)(1) is redesignated as paragraph (d)(2)(i).
f. In paragraph (d)(2)(i), the first sentence is amended by
revising the words ``1 Mg/yr'' to read ``1 Mg/yr (1.1 ton/yr).''
g. In paragraph (e)(2)(i), the first sentence is amended by
revising the words ``6.0 Mg/yr'' to read ``6.0 Mg/yr (6.6 ton/yr).''

Sec. 61.348 [Amended]

56. Amend Sec. 61.348 as follows:
a. In paragraph (b)(2)(ii), the first sentence is amended by
revising the words ``1 Mg/yr'' to read ``1 Mg/yr (1.1 ton/yr).''
b. In paragraph (b)(2)(ii)(B), by revising the third sentence.
The revision reads as follows:

Sec. 61.348 Standards: Treatment processes.

(b) * * *
(2) * * *
(ii) * * *
(B) * * * An enhanced biodegradation unit typically operates at a
food-to-microorganism ratio in the range of 0.05 to 1.0 kg of
biological oxygen demand per kg of biomass per day, a mixed liquor
suspended solids ratio in the range of 1 to 8 grams per liter (0.008 to
0.7 pounds per liter), and a residence time in the range of 3 to 36
hours.
* * * * *

Sec. 61.349 [Amended]

57. In Sec. 61.349, paragraph (a)(2)(i)(C) is amended by revising
the words ``760 deg.C'' to read ``760 deg.C (1,400 deg.F).''

Sec. 61.354 [Amended]

58. In Sec. 61.354, paragraph (c)(4) is amended by revising the
words ``44 megawatts (MW)'' to read ``44 MW (150 x 106
BTU/hr).''

58a. In paragraph (c)(5), ``44 MW'' is revised to read ``44 MW (150
x 106 BTU/hr).''

Sec. 61.355 [Amended]

59. Amend Sec. 61.355 as follows:
a. Paragraphs (a)(3), (a)(4), (a)(4)(ii) are amended by revising
the words ``10 Mg/yr'' to read ``10 Mg/yr (11 ton/yr)'' wherever they
occur.
b. Paragraphs (a)(4), (a)(5), and (a)(5)(ii) are amended by
revising the words ``1 Mg/yr'' to read ``1 Mg/yr (1.1 ton/yr)''
wherever they occur.
c. Paragraphs (c)(3)(ii)(F) and (c)(3)(ii)(H) are amended by
revising the words ``10 deg.C'' to read ``10 deg.C (50 deg.F)''
wherever they occur.
d. Paragraph (c)(3)(v) is amended by revising the words ``kg/yr''
to read ``kg/yr (lb/yr)'' wherever they occur.
e. Paragraphs (e)(3), (e)(4), (f)(3), (f)(4)(iv), (f)(5),
(i)(3)(iv), and (i)(4) are amended by revising the definitions of the
terms used in the equations; and (f)(4)(iii) and (i)(3)(iii) are
amended by revising the equation and definitions of terms used in the
equations.
f. Paragraphs (f)(4)(ii)(B), (f)(4)(ii)(C), (h)(1), (h)(2), (h)(3),
(h)(5), (h)(6), (i)(2), (i)(3)(ii)(B), and (i)(3)(ii)(C) are amended by
revising the word ``method'' to read ``Method'' wherever it occurs.
g. Paragraph (k)(7) is amended by revising the words ``6.0 Mg/yr''
to read ``6.0 Mg/yr (6.6 ton/yr).''
The revisions read as follows:

Sec. 61.355 Test methods, procedures, and compliance provisions.

* * * * *
(e) * * *
(3) * * *

Eb = Mass flow rate of benzene entering the treatment
process, kg/hr (lb/hr).
K = Density of the waste stream, kg/m\3\ (lb/ft\3\).
Vi = Average volume flow rate of waste entering the
treatment process during each run i, m\3\/hr (ft\3\/hr).
Ci = Average concentration of benzene in the waste stream
entering the treatment process during each run i, ppmw.
n = Number of runs.
106 = Conversion factor for ppmw.

(4) * * *
Ea = Mass flow rate of benzene exiting the treatment
process, kg/hr (lb/hr).
K = Density of the waste stream, kg/m3 (lb/ft3).
Vi = Average volume flow rate of waste exiting the treatment
process during each run i, m3/hr (ft3/hr).
Ci = Average concentration of benzene in the waste stream
exiting the treatment process during each run i, ppmw.
n = Number of runs.
106 = Conversion factor for ppmw.

(f) * * *
(3) * * *

Eb = Mass flow rate of benzene entering the combustion unit,
kg/hr (lb/hr).
K = Density of the waste stream, kg/m3 (lb/ft3).
Vi = Average volume flow rate of waste entering the
combustion unit during each run i, m3/hr (ft3/
hr).
Ci = Average concentration of benzene in the waste stream
entering the combustion unit during each run i, ppmw.
n = Number of runs.
106 = Conversion factor for ppmw.

(4) * * *
(iii) * * *
[GRAPHIC] [TIFF OMITTED] TR17OC00.488

Where:

Mi = Mass of benzene emitted during run i, kg (lb).
V = Volume of air-vapor mixture exhausted at standard conditions,
m3 (ft3).
C = Concentration of benzene measured in the exhaust, ppmv.
Db = Density of benzene, 3.24 kg/m3 (0.202 lb/
ft3).
106 = Conversion factor for ppmv.
(iv) * * *
Ea = Mass flow rate of benzene emitted from the combustion
unit, kg/hr (lb/hr).
Mi = Mass of benzene emitted from the combustion unit during
run i, kg (lb).
T = Total time of all runs, hr.
n = Number of runs.

(5) * * *

R = Benzene destruction efficiency for the combustion unit, percent.
Eb = Mass flow rate of benzene entering the combustion unit,
kg/hr (lb/hr).
Ea = Mass flow rate of benzene emitted from the combustion
unit, kg/hr (lb/hr).
* * * * *
(i) * * *
(3) * * *
(iii) * * *
[GRAPHIC] [TIFF OMITTED] TR17OC00.489

[GRAPHIC] [TIFF OMITTED] TR17OC00.490

Maj = Mass of organics or benzene in the vent stream
entering the control device during run j, kg (lb).
Mbj = Mass of organics or benzene in the vent stream exiting
the control device during run j, kg (lb).
Vaj = Volume of vent stream entering the control device
during run j, at standard conditions, m3 (ft3).
Vbj = Volume of vent stream exiting the control device
during run j, at standard conditions, m3 (ft3).
Cai = Organic concentration of compound i or the benzene
concentration measured in the vent stream entering the control device
as determined by Method 18, ppm by volume on a dry basis.
Cbi = Organic concentration of compound i or the benzene
concentration measured in the vent stream exiting the control device as
determined by Method 18, ppm by volume on a dry basis.
MWi = Molecular weight of organic compound i in the vent
stream, or the molecular weight of benzene, kg/kg-mol (lb/lb-mole).

[[Page 62161]]

n = Number of organic compounds in the vent stream; if benzene
reduction efficiency is being demonstrated, then n=1.
K1 = Conversion factor for molar volume at standard
conditions (293 K and 760 mm Hg (527 R and 14.7 psia))
= 0.0416 kg-mol/m3 (0.00118 lb-mol/ft3)
10-6=Conversion factor for ppmv.

(iv) * * *

Ea = Mass flow rate of organics or benzene entering the
control device, kg/hr (lb/hr).
Eb = Mass flow rate of organics or benzene exiting the
control device, kg/hr (lb/hr).
Maj = Mass of organics or benzene in the vent stream
entering the control device during run j, kg (lb).
M bj = Mass of organics or benzene in the vent stream
exiting the control device during run j, kg (lb).
T = Total time of all runs, hr.
n = Number of runs.
(4) * * *
R = Total organic reduction of efficiency or benzene reduction
efficiency for the control device, percent.
Eb = Mass flow rate of organics or benzene entering the
control device, kg/hr (lb/hr).
Ea = Mass flow rate of organic or benzene emitted from the
control device, kg/hr (lb/hr).
* * * * *

Sec. 61.356 [Amended]

60. Amend Sec. 61.356 as follows:
a. Paragraph (b)(2)(i) is amended by revising the words ``0.02
liters per minute'' to read ``0.02 liters (0.005 gallons) per minute.''
b. Paragraph (b)(2)(i) is amended by revising the words ``10 Mg/
yr'' to read ``10 Mg/yr (11 ton/yr).''
c. Paragraph (b)(2)(ii) is amended by revising the words ``2.0 Mg/
yr'' to read ``2.0 Mg/yr (2.2 ton/yr).''
d. Paragraph (b)(4) is amended by revising the words ``6.0 Mg/yr''
to read ``6.0 Mg/yr (6.6 ton/yr).''
e. Paragraphs (j)(4), (j)(5), and (j)(6) are amended by revising
the words ``28 deg.C'' to read ``28 deg.C (50 deg.F)'' wherever they
occur.
f. Paragraph (j)(6) is amended by revising the words ``44 MW'' to
read ``44 MW (150 x 106 BTU/hr)'' wherever they occur.
g. Paragraph (j)(8) is amended by revising the words ``6 deg.C''
to read ``6 deg.C (11 deg.F)'' wherever they occur.

Sec. 61.357 [Amended]

61. Amend Sec. 61.357 as follows:
a. Paragraphs (b) and (c) are amended by revising the words ``1 Mg/
yr'' to read ``1 Mg/yr (1.1 ton/yr)'' wherever they occur.
b. Paragraphs (c) and (d) are amended by revising the words ``10
Mg/yr'' to read ``10 Mg/yr (11 ton/yr)'' wherever they occur.
c. Paragraphs (d)(7)(iv)(A), (d)(7)(iv)(B), and (d)(7)(iv)(C) are
amended by revising the words ``28 deg.C'' to read ``28 deg.C (50
deg.F)'' wherever they occur.
d. Paragraph (d)(7)(iv)(C) is amended by revising the words ``44
MW'' to read ``44 MW (150 x 106 BTU/hr).''
e. Paragraph (d)(7)(iv)(E) is amended by revising the words ``6
deg.C'' to read ``6 deg.C (11 deg.F).''

62. In Part 61, Appendix B is amended by revising Methods 101,
101A, 102, 103, 104, 105, 106, 107, 107A, 108, 108A, 108B, 108C, and
111 to read as follows:

Method 101--Determination of Particulate and Gaseous Mercury
Emissions From Chlor-Alkali Plants (Air Streams)

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 methods in Appendix A to 40 CFR Part
60. Therefore, to obtain reliable results, persons using this method
should have a thorough knowledge of at least the following
additional test methods: Method 1, Method 2, Method 3, and Method 5.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Mercury (Hg)...................... 7439-97-6 Dependent upon
recorder and
spectrophotometer.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of Hg emissions, including both particulate and gaseous Hg, from chlor-
alkali plants and other sources (as specified in the regulations) where
the carrier-gas stream in the duct or stack is principally air.
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

Particulate and gaseous Hg emissions are withdrawn isokinetically
from the source and collected in acidic iodine monochloride (ICl)
solution. The Hg collected (in the mercuric form) is reduced to
elemental Hg, which is then aerated from the solution into an optical
cell and measured by atomic absorption spectrophotometry.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Sample Collection. Sulfur dioxide (SO2) reduces ICl
and causes premature depletion of the ICl solution.
4.2 Sample Analysis.
4.2.1 ICl concentrations greater than 10-4 molar
inhibit the reduction of the Hg (II) ion in the aeration cell.
4.2.2 Condensation of water vapor on the optical cell windows
causes a positive interference.

5.0 Safety

5.1 Disclaimer. This method may involve hazardous materials,
operations, and equipment. This test method does not purport to address
all of the safety problems associated with its use. It is the
responsibility of the user of this test method to establish appropriate
safety and health practices and determine the applicability of
regulatory limitations prior to performing this test method.
5.2 Corrosive Reagents. The following reagents are hazardous.
Personal protective equipment and safe procedures are useful in
preventing chemical splashes. If contact occurs, immediately flush with
copious amounts of water for at least 15 minutes. Remove clothing under
shower and decontaminate. Treat residual chemical burn as thermal burn.
5.2.1 Hydrochloric Acid (HCl). Highly toxic and corrosive. Causes
severe damage to tissues. 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.
5.2.2 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

[[Page 62162]]

still be fatal. Provide ventilation to limit exposure. Strong oxidizer.
Hazardous reaction may occur with organic materials such as solvents.
5.2.3 Sulfuric Acid (H2SO4). Rapidly
destructive to body tissue. Will cause third degree burns. Eye damage
may result in blindness. Inhalation may be fatal from spasm of the
larynx, usually within 30 minutes. 3 mg/m3 will cause lung
damage. 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.

6.0 Equipment and Supplies.

6.1 Sample Collection. A schematic of the sampling train used in
performing this method is shown in Figure 101-1; it is similar to the
Method 5 sampling train. The following items are required for sample
collection:
6.1.1 Probe Nozzle, Pitot Tube, Differential Pressure Gauge,
Metering System, Barometer, and Gas Density Determination Equipment.
Same as Method 5, Sections 6.1.1.1, 6.1.1.3, 6.1.1.4, 6.1.1.9, 6.1.2,
and 6.1.3, respectively.
6.1.2 Probe Liner. Borosilicate or quartz glass tubing. A heating
system capable of maintaining a gas temperature of 120 14
deg.C (248 25 deg.F) at the probe exit during sampling
may be used to prevent water condensation.

Note: Do not use metal probe liners.

6.1.3 Impingers. Four Greenburg-Smith impingers connected in
series with leak-free ground glass fittings or any similar leak-free
noncontaminating fittings. For the first, third, and fourth impingers,
impingers that are modified by replacing the tip with a 13-mm ID (0.5-
in.) glass tube extending to 13 mm (0.5 in.) from the bottom of the
flask may be used.
6.1.4 Acid Trap. Mine Safety Appliances air line filter, Catalog
number 81857, with acid absorbing cartridge and suitable connections,
or equivalent.
6.2 Sample Recovery. The following items are needed for sample
recovery:
6.2.1 Glass Sample Bottles. Leakless, with Teflon-lined caps,
1000- and 100-ml.
6.2.2 Graduated Cylinder. 250-ml.
6.2.3 Funnel and Rubber Policeman. To aid in transfer of silica
gel to container; not necessary if silica gel is weighed in the field.
6.2.4 Funnel. Glass, to aid in sample recovery.
6.3 Sample Preparation and Analysis. The following items are
needed for sample preparation and analysis:
6.3.1 Atomic Absorption Spectrophotometer. Perkin-Elmer 303, or
equivalent, containing a hollow-cathode mercury lamp and the optical
cell described in Section 6.3.2.
6.3.2 Optical Cell. Cylindrical shape with quartz end windows and
having the dimensions shown in Figure 101-2. Wind the cell with
approximately 2 meters (6 ft) of 24-gauge Nichrome wire, or equivalent,
and wrap with fiberglass insulation tape, or equivalent; do not let the
wires touch each other.
6.3.3 Aeration Cell. Constructed according to the specifications
in Figure 101-3. Do not use a glass frit as a substitute for the blown
glass bubbler tip shown in Figure 101-3.
6.3.4 Recorder. Matched to output of the spectrophotometer
described in Section 6.3.1.
6.3.5 Variable Transformer. To vary the voltage on the optical
cell from 0 to 40 volts.
6.3.6 Hood. For venting optical cell exhaust.
6.3.7 Flow Metering Valve.
6.3.8 Rate Meter. Rotameter, or equivalent, capable of measuring
to within 2 percent a gas flow of 1.5 liters/min (0.053 cfm).
6.3.9 Aeration Gas Cylinder. Nitrogen or dry, Hg-free air,
equipped with a single-stage regulator.
6.3.10 Tubing. For making connections. Use glass tubing (ungreased
ball and socket connections are recommended) for all tubing connections
between the solution cell and the optical cell; do not use Tygon
tubing, other types of flexible tubing, or metal tubing as substitutes.
Teflon, steel, or copper tubing may be used between the nitrogen tank
and flow metering valve (Section 6.3.7), and Tygon, gum, or rubber
tubing between the flow metering valve and the aeration cell.
6.3.11 Flow Rate Calibration Equipment. Bubble flow meter or wet-
test meter for measuring a gas flow rate of 1.5 0.1
liters/min (0.053 0.0035 cfm).
6.3.12 Volumetric Flasks. Class A with penny head standard taper
stoppers; 100-, 250-, 500-, and 1000-ml.
6.3.13 Volumetric Pipets. Class A; 1-, 2-, 3-, 4-, and 5-ml.
6.3.14 Graduated Cylinder. 50-ml.
6.3.15 Magnetic Stirrer. General-purpose laboratory type.
6.3.16 Magnetic Stirring Bar. Teflon-coated.
6.3.17 Balance. Capable of weighing to 0.5 g.
6.3.18 Alternative Analytical Apparatus. Alternative systems are
allowable as long as they meet the following criteria:
6.3.18.1 A linear calibration curve is generated and two
consecutive samples of the same aliquot size and concentration agree
within 3 percent of their average.
6.3.18.2 A minimum of 95 percent of the spike is recovered when an
aliquot of a source sample is spiked with a known concentration of Hg
(II) compound.
6.3.18.3 The reducing agent should be added after the aeration
cell is closed.
6.3.18.4 The aeration bottle bubbler should not contain a frit.
6.3.18.5 Any Tygon tubing used should be as short as possible and
conditioned prior to use until blanks and standards yield linear and
reproducible results.
6.3.18.6 If manual stirring is done before aeration, it should be
done with the aeration cell closed.
6.3.18.7 A drying tube should not be used unless it is conditioned
as the Tygon tubing above.

7.0 Reagents and Standards

Unless otherwise indicated, all reagents must conform to the
specifications established by the Committee on Analytical Reagents of
the American Chemical Society; where such specifications are not
available, use the best available grade.
7.1 Sample Collection. The following reagents are required for
sample collection:
7.1.1 Water. Deionized distilled, to conform to ASTM D 1193-77 or
91 (incorporated by reference--see Sec. 61.18), Type 1. If high
concentrations of organic matter are not expected to be present, the
analyst may eliminate the KMnO4 test for oxidizable organic
matter. Use this water in all dilutions and solution preparations.
7.1.2 Nitric Acid, 50 Percent (v/v). Mix equal volumes of
concentrated HNO3 and water, being careful to add the acid
to the water slowly.
7.1.3 Silica Gel. Indicating type, 6- to 16-mesh. If previously
used, dry at 175 deg.C (350 deg.F) for 2 hours. The tester may use
new silica gel as received.
7.1.4 Potassium Iodide (KI) Solution, 25 Percent. Dissolve 250 g
of KI in water, and dilute to 1 liter.
7.1.5 Iodine Monochloride Stock Solution, 1.0 M. To 800 ml of 25
percent KI solution, add 800 ml of concentrated HCl. Cool to room
temperature. With vigorous stirring, slowly add 135 g of potassium
iodate (KIO3), and stir until all free iodine has dissolved.
A clear orange-red solution occurs when all the KIO3 has
been added. Cool to room temperature, and dilute to 1800 ml with

[[Page 62163]]

water. Keep the solution in amber glass bottles to prevent degradation.
7.1.6 Absorbing Solution, 0.1 M ICl. Dilute 100 ml of the 1.0 M
ICl stock solution to 1 liter with water. Keep the solution in amber
glass bottles and in darkness to prevent degradation. This reagent is
stable for at least two months.
7.2 Sample Preparation and Analysis. The following reagents and
standards are required for sample preparation and analysis:
7.2.1 Reagents.
7.2.1.1 Tin (II) Solution. Prepare fresh daily, and keep sealed
when not being used. Completely dissolve 20 g of tin (II) chloride (or
25 g of tin (II) sulfate) crystals (Baker Analyzed reagent grade or any
other brand that will give a clear solution) in 25 ml of concentrated
HCl. Dilute to 250 ml with water. Do not substitute HNO3,
H2SO4, or other strong acids for the HCl.
7.2.1.2 Sulfuric Acid, 5 Percent (v/v). Dilute 25 ml of
concentrated H2SO4 to 500 ml with water.
7.2.2 Standards
7.2.2.1 Hg Stock Solution, 1 mg Hg/ml. Prepare and store all Hg
standard solutions in borosilicate glass containers. Completely
dissolve 0.1354 g of Hg (II) chloride in 75 ml of water in a 100-ml
glass volumetric flask. Add 10 ml of concentrated HNO3, and
adjust the volume to exactly 100 ml with water. Mix thoroughly. This
solution is stable for at least one month.
7.2.2.2 Intermediate Hg Standard Solution, 10 g Hg/ml.
Prepare fresh weekly. Pipet 5.0 ml of the Hg stock solution (Section
7.2.2.1) into a 500-ml glass volumetric flask, and add 20 ml of the 5
percent H2SO4 solution. Dilute to exactly 500 ml
with water. Thoroughly mix the solution.
7.2.2.3 Working Hg Standard Solution, 200 ng Hg/ml. Prepare fresh
daily. Pipet 5.0 ml of the intermediate Hg standard solution (Section
7.2.2.2) into a 250-ml volumetric glass flask. Add 10 ml of the 5
percent H2SO4 and 2 ml of the 0.1 M ICl absorbing
solution taken as a blank (Section 8.7.4.3), and dilute to 250 ml with
water. Mix thoroughly.

8.0 Sample Collection, Preservation, Transport, and Storage

Because of the complexity of this method, testers should be trained
and experienced with the test procedures to ensure reliable results.
Since the amount of Hg that is collected generally is small, the method
must be carefully applied to prevent contamination or loss of sample.
8.1 Pretest Preparation. Follow the general procedure outlined in
Method 5, Section 8.1, except omit Sections 8.1.2 and 8.1.3.
8.2 Preliminary Determinations. Follow the general procedure
outlined in Method 5, Section 8.2, with the exception of the following:
8.2.1 Select a nozzle size based on the range of velocity heads to
assure that it is not necessary to change the nozzle size in order to
maintain isokinetic sampling rates below 28 liters/min (1.0 cfm).
8.2.2 Perform test runs such that samples are obtained over a
period or periods that accurately determine the maximum emissions that
occur in a 24-hour period. In the case of cyclic operations, run
sufficient tests for the accurate determination of the emissions that
occur over the duration of the cycle. A minimum sample time of 2 hours
is recommended. In some instances, high Hg or high SO2
concentrations make it impossible to sample for the desired minimum
time. This is indicated by reddening (liberation of free iodine) in the
first impinger. In these cases, the sample run may be divided into two
or more subruns to ensure that the absorbing solution is not depleted.
8.3 Preparation of Sampling Train.
8.3.1 Clean all glassware (probe, impingers, and connectors) by
rinsing with 50 percent HNO3, tap water, 0.1 M ICl, tap
water, and finally deionized distilled water. Place 100 ml of 0.1 M ICl
in each of the first three impingers. Take care to prevent the
absorbing solution from contacting any greased surfaces. Place
approximately 200 g of preweighed silica gel in the fourth impinger.
More silica gel may be used, but care should be taken to ensure that it
is not entrained and carried out from the impinger during sampling.
Place the silica gel container in a clean place for later use in the
sample recovery. Alternatively, determine and record the weight of the
silica gel plus impinger to the nearest 0.5 g.
8.3.2 Install the selected nozzle using a Viton A O-ring when
stack temperatures are less than 260 deg.C (500 deg.F). Use a
fiberglass string gasket if temperatures are higher. See APTD-0576
(Reference 3 in Method 5) for details. Other connecting systems using
either 316 stainless steel or Teflon ferrules may be used. Mark the
probe with heat-resistant tape or by some other method to denote the
proper distance into the stack or duct for each sampling point.
8.3.3 Assemble the train as shown in Figure 101-1, using (if
necessary) a very light coat of silicone grease on all ground glass
joints. Grease only the outer portion (see APTD-0576) to avoid the
possibility of contamination by the silicone grease.

Note: An empty impinger may be inserted between the third
impinger and the silica gel to remove excess moisture from the
sample stream.

8.3.4 After the sampling train has been assembled, turn on and set
the probe heating system, if applicable, at the desired operating
temperature. Allow time for the temperatures to stabilize. Place
crushed ice around the impingers.
8.4 Leak-Check Procedures. Follow the leak-check procedures
outlined in Method 5, Section 8.4.
8.5 Sampling Train Operation. Follow the general procedure
outlined in Method 5, Section 8.5. For each run, record the data
required on a data sheet such as the one shown in Figure 101-4.
8.6 Calculation of Percent Isokinetic. Same as Method 5, Section
8.6.
8.7 Sample Recovery. Begin proper cleanup procedure as soon as the
probe is removed from the stack at the end of the sampling period.
8.7.1 Allow the probe to cool. When it can be safely handled, wipe
off any external particulate matter near the tip of the probe nozzle,
and place a cap over it. Do not cap off the probe tip tightly while the
sampling train is cooling. Capping would create a vacuum and draw
liquid out from the impingers.
8.7.2 Before moving the sampling train to the cleanup site, remove
the probe from the train, wipe off the silicone grease, and cap the
open outlet of the probe. Be careful not to lose any condensate that
might be present. Wipe off the silicone grease from the impinger. Use
either ground-glass stoppers, plastic caps, or serum caps to close
these openings.
8.7.3 Transfer the probe and impinger assembly to a cleanup area
that is clean, protected from the wind, and free of Hg contamination.
The ambient air in laboratories located in the immediate vicinity of
Hg-using facilities is not normally free of Hg contamination.
8.7.4 Inspect the train before and during disassembly, and note
any abnormal conditions. Treat the samples as follows.
8.7.4.1 Container No. 1 (Impingers and Probe).
8.7.4.1.1 Using a graduated cylinder, measure the liquid in the
first three impingers to within 1 ml. Record the volume of liquid
present (e.g., see Figure 5-6 of Method 5). This information is needed
to calculate the moisture content of the effluent gas.

[[Page 62164]]

(Use only glass storage bottles and graduated cylinders that have been
precleaned as in Section 8.3.1) Place the contents of the first three
impingers into a 1000-ml glass sample bottle.
8.7.4.1.2 Taking care that dust on the outside of the probe or
other exterior surfaces does not get into the sample, quantitatively
recover the Hg (and any condensate) from the probe nozzle, probe
fitting, and probe liner as follows: Rinse these components with two
50-ml portions of 0.1 M ICl. Next, rinse the probe nozzle, fitting and
liner, and each piece of connecting glassware between the probe liner
and the back half of the third impinger with a maximum of 400 ml of
water. Add all washings to the 1000-ml glass sample bottle containing
the liquid from the first three impingers.
8.7.4.1.3 After all washings have been collected in the sample
container, tighten the lid on the container to prevent leakage during
shipment to the laboratory. Mark the height of the liquid to determine
later whether leakage occurred during transport. Label the container to
identify clearly its contents.
8.7.4.2 Container No. 2 (Silica Gel). Same as Method 5, Section
8.7.6.3.
8.7.4.3 Container No. 3 (Absorbing Solution Blank). Place 50 ml of
the 0.1 M ICl absorbing solution in a 100-ml sample bottle. Seal the
container. Use this blank to prepare the working Hg standard solution
(Section 7.2.2.3).

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.4 10.2...................... Sampling Ensure accuracy and
equipment leak- precision of
checks and sampling
calibration. measurements.
10.5, 10.6.................... Spectrophotometer Ensure linearity of
calibration. spectrophotometer
response to
standards.
11.3.3........................ Check for matrix Eliminate matrix
effects. effects.
------------------------------------------------------------------------

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

10.0 Calibration and Standardizations

Note: Maintain a laboratory log of all calibrations.

10.1 Before use, clean all glassware, both new and used, as
follows: brush with soap and tap water, liberally rinse with tap water,
soak for 1 hour in 50 percent HNO3, and then rinse with
deionized distilled water.
10.2 Sampling Equipment. Calibrate the sampling equipment
according to the procedures outlined in the following sections of
Method 5: Section 10.1 (Probe Nozzle), Section 10.2 (Pitot Tube
Assembly), Section 10.3 (Metering System), Section 10.5 (Temperature
Sensors), Section 10.6 (Barometer).
10.3 Aeration System Flow Rate Meter. Assemble the aeration system
as shown in Figure 101-5. Set the outlet pressure on the aeration gas
cylinder regulator to a minimum pressure of 500 mm Hg (10 psi), and use
the flow metering valve and a bubble flowmeter or wet-test meter to
obtain a flow rate of 1.5 0.1 liters/min (0.053
0.0035 cfm) through the aeration cell. After the
calibration of the aeration system flow rate meter is complete, remove
the bubble flowmeter from the system.
10.4 Optical Cell Heating System. Using a 50-ml graduated
cylinder, add 50 ml of water to the bottle section of the aeration
cell, and attach the bottle section to the bubbler section of the cell.
Attach the aeration cell to the optical cell and while aerating at 1.5
0.1 liters/min (0.053 0.0035 cfm), determine
the minimum variable transformer setting necessary to prevent
condensation of moisture in the optical cell and in the connecting
tubing. (This setting should not exceed 20 volts.)
10.5 Spectrophotometer and Recorder.
10.5.1 The Hg response may be measured by either peak height or
peak area.

Note: The temperature of the solution affects the rate at which
elemental Hg is released from a solution and, consequently, it
affects the shape of the absorption curve (area) and the point of
maximum absorbance (peak height). Therefore, to obtain reproducible
results, bring all solutions to room temperature before use.

10.5.2 Set the spectrophotometer wavelength at 253.7 nm, and make
certain the optical cell is at the minimum temperature that will
prevent water condensation. Then set the recorder scale as follows:
Using a 50-ml graduated cylinder, add 50 ml of water to the aeration
cell bottle. Add three drops of Antifoam B to the bottle, and then
pipet 5.0 ml of the working Hg standard solution into the aeration
cell.

Note: Always add the Hg-containing solution to the aeration cell
after the 50 ml of water.

10.5.3 Place a Teflon-coated stirring bar in the bottle. Before
attaching the bottle section to the bubbler section of the aeration
cell, make certain that (1) the aeration cell exit arm stopcock (Figure
101-3) is closed (so that Hg will not prematurely enter the optical
cell when the reducing agent is being added) and (2) there is no flow
through the bubbler. If conditions (1) and (2) are met, attach the
bottle section to the bubbler section of the aeration cell. Pipet 5 ml
of tin (II) reducing solution into the aeration cell through the side
arm, and immediately stopper the side arm. Stir the solution for 15
seconds, turn on the recorder, open the aeration cell exit arm
stopcock, and immediately initiate aeration with continued stirring.
Determine the maximum absorbance of the standard, and set this value to
read 90 percent of the recorder full scale.
10.6 Calibration Curve.
10.6.1 After setting the recorder scale, repeat the procedure in
Section 10.5 using 0.0-, 1.0-, 2.0-, 3.0-, 4.0-, and 5.0-ml aliquots of
the working standard solution (final amount of Hg in the aeration cell
is 0, 200, 400, 600, 800, and 1000 ng, respectively). Repeat this
procedure on each aliquot size until two consecutive peaks agree within
3 percent of their average value.

Note: To prevent Hg carryover from one sample to another, do not
close the aeration cell from the optical cell until the recorder pen
has returned to the baseline.)

10.6.2 It should not be necessary to disconnect the aeration gas
inlet line from the aeration cell when changing samples. After
separating the bottle and bubbler sections of the aeration cell, place
the bubbler section into a 600-ml beaker containing approximately 400
ml of water. Rinse the bottle section of the aeration cell with a
stream of water to remove all traces of the tin (II) reducing agent.
Also, to prevent the loss of Hg before aeration, remove all traces of
the reducing agent between samples by washing with water. It will be
necessary, however, to wash the aeration cell parts with concentrated
HCl if any of the following conditions occur: (1) A white film appears
on any inside surface of the aeration cell, (2) the calibration curve
changes suddenly, or (3) the replicate samples do not yield
reproducible results.
10.6.3 Subtract the average peak height (or peak area) of the
blank (0.0-ml aliquot)--which must be less than 2 percent of recorder
full scale--from the averaged peak heights of the 1.0-, 2.0-, 3.0-,
4.0-, and 5.0-ml aliquot standards. If the blank absorbance is greater
than 2 percent of full-scale, the probable

[[Page 62165]]

cause is Hg contamination of a reagent or carry-over of Hg from a
previous sample. Prepare the calibration curve by plotting the
corrected peak height of each standard solution versus the
corresponding final total Hg weight in the aeration cell (in ng), and
draw the best fit straight line. This line should either pass through
the origin or pass through a point no further from the origin than
2 percent of the recorder full scale. If the line does not
pass through or very near to the origin, check for nonlinearity of the
curve and for incorrectly prepared standards.

11.0 Analytical Procedure

11.1 Sample Loss Check. Check the liquid level in each container
to see whether liquid was lost during transport. If a noticeable amount
of leakage occurred, either void the sample or use methods subject to
the approval of the Administrator to account for the losses.
11.2 Sample Preparation. Treat each sample as follows:
11.2.1 Container No. 1 (Impingers and Probe). Carefully transfer
the contents of Container No. 1 into a 1000-ml volumetric flask, and
adjust the volume to exactly 1000 ml with water.
11.2.2 Dilutions. Pipet a 2-ml aliquot from the diluted sample
from Section 11.2.1 into a 250-ml volumetric flask. Add 10 ml of 5
percent H2SO4, and adjust the volume to exactly
250 ml with water. This solution is stable for at least 72 hours.

Note: The dilution factor will be 250/2 for this solution.

11.3 Analysis. Calibrate the analytical equipment and develop a
calibration curve as outlined in Sections 10.3 through 10.6.
11.3.1 Mercury Samples. Repeat the procedure used to establish the
calibration curve with an appropriately sized aliquot (1 to 5 ml) of
the diluted sample (from Section 11.2.2) until two consecutive peak
heights agree within 3 percent of their average value. The peak maximum
of an aliquot (except the 5-ml aliquot) must be greater than 10 percent
of the recorder full scale. If the peak maximum of a 1.0-ml aliquot is
off scale on the recorder, further dilute the original source sample to
bring the Hg concentration into the calibration range of the
spectrophotometer.
11.3.2 Run a blank and standard at least after every five samples
to check the spectrophotometer calibration. The peak height of the
blank must pass through a point no further from the origin than
2 percent of the recorder full scale. The difference
between the measured concentration of the standard (the product of the
corrected peak height and the reciprocal of the least squares slope)
and the actual concentration of the standard must be less than 7
percent, or recalibration of the analyzer is required.
11.3.3 Check for Matrix Effects (optional). Use the Method of
Standard Additions as follows to check at least one sample from each
source for matrix effects on the Hg results. The Method of Standard
Additions procedures described on pages 9-4 and 9-5 of the section
entitled ``General Information'' of the Perkin Elmer Corporation Atomic
Absorption Spectrophotometry Manual, Number 303-0152 (Reference 16 in
Section 16.0) are recommended. If the results of the Method of Standard
Additions procedure used on the single source sample do not agree to
within 5 percent of the value obtained by the routine
atomic absorption analysis, then reanalyze all samples from the source
using the Method of Standard Additions procedure.
11.4 Container No. 2 (Silica Gel). Weigh the spent silica gel (or
silica gel plus impinger) to the nearest 0.5 g using a balance. (This
step may be conducted in the field.)

12.0 Data Analysis and Calculations

Carry out calculations, retaining at least one extra decimal
significant figure beyond that of the acquired data. Round off figures
only after the final calculation. Other forms of the equations may be
used as long as they give equivalent results.
12.1 Average Dry Gas Meter Temperature and Average Orifice
Pressure Drop, Dry Gas Volume, Volume of Water Vapor Condensed,
Moisture Content, and Isokinetic Variation. Same as Method 5, Sections
12.2 through 12.5 and 12.11, respectively.
12.2 Stack Gas Velocity. Using the data from this test and
Equation 2-9 of Method 2, calculate the average stack gas velocity
vs.
12.3 Total Mercury.
12.3.1 For each source sample, correct the average maximum
absorbance of the two consecutive samples whose peak heights agree
within 3 percent of their average for the contribution of the solution
blank (see Section 10.6.3). Use the calibration curve and these
corrected averages to determine the final total weight of Hg in ng in
the aeration cell for each source sample.
12.3.2 Correct for any dilutions made to bring the sample into the
working range of the spectrophotometer. Then calculate the Hg in the
original solution, mHg, as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.491

Where:

CHg(AC) = Total ng of Hg in aliquot analyzed (reagent blank
subtracted).
DF = Dilution factor for the Hg-containing solution (before adding to
the aeration cell; e.g., DF = 250/2 if the source samples were diluted
as described in Section 11.2.2).
Vf = Solution volume of original sample, 1000 ml for samples
diluted as described in Section 11.2.1.
10-\3\ = Conversion factor, g/ng.
S = Aliquot volume added to aeration cell, ml.

12.4 Mercury Emission Rate. Calculate the daily Hg emission rate,
R, using Equation 101-2. For continuous operations, the operating time
is equal to 86,400 seconds per day. For cyclic operations, use only the
time per day each stack is in operation. The total Hg emission rate
from a source will be the summation of results from all stacks.
[GRAPHIC] [TIFF OMITTED] TR17OC00.492

Where:

K1 = 0.3858 deg.K/mm Hg for metric units.
K1 = 17.64 deg.R/in. Hg for English units.

[[Page 62166]]

K3 = 10-6 g/g for metric units.
= 2.2046 `` x 10-9 lb/g for English units.
Ps = Absolute stack gas pressure, mm Hg (in. Hg).
t = Daily operating time, sec/day.
Ts = Absolute average stack gas temperature, deg.K
( deg.R).
Vm(std) = Dry gas sample volume at standard conditions, scm
(scf).
Vw(std) = Volume of water vapor at standard conditions, scm
(scf).

12.5 Determination of Compliance. Each performance test consists
of three repetitions of the applicable test method. For the purpose of
determining compliance with an applicable national emission standard,
use the average of the results of all repetitions.

13.0 Method Performance

The following estimates are based on collaborative tests, wherein
13 laboratories performed duplicate analyses on two Hg-containing
samples from a chlor-alkali plant and on one laboratory-prepared sample
of known Hg concentration. The sample concentrations ranged from 2 to
65 g Hg/ml.
13.1 Precision. The estimated intra-laboratory and inter-
laboratory standard deviations are 1.6 and 1.8 g Hg/ml,
respectively.
13.2 Accuracy. The participating laboratories that analyzed a 64.3
g Hg/ml (in 0.1 M ICl) standard obtained a mean of 63.7
g Hg/ml.
13.3 Analytical Range. After initial dilution, the range of this
method is 0.5 to 120 g Hg/ml. The upper limit can be extended
by further dilution of the sample.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

Same as Method 5, Section 17.0, References 1-3, 5, and 6, with the
addition of the following:

1. Determining Dust Concentration in a Gas Stream. ASME
Performance Test Code No. 27. New York, NY. 1957.
2. DeVorkin, Howard, et al. Air Pollution Source Testing Manual.
Air Pollution Control District. Los Angeles, CA. November 1963.
3. Hatch, W.R., and W.I. Ott. Determination of Sub-Microgram
Quantities of Mercury by Atomic Absorption Spectrophotometry. Anal.
Chem. 40:2085-87. 1968.
4. Mark, L.S. Mechanical Engineers' Handbook. McGraw-Hill Book
Co., Inc. New York, NY. 1951.
5. Western Precipitation Division of Joy Manufacturing Co.
Methods for Determination of Velocity, Volume, Dust and Mist Content
of Gases. Bulletin WP-50. Los Angeles, CA. 1968.
6. Perry, J.H. Chemical Engineers' Handbook. McGraw-Hill Book
Co., Inc. New York, NY. 1960.
7. Shigehara, R.T., W.F. Todd, and W.S. Smith. Significance of
Errors in Stack Sampling Measurements. Stack Sampling News. 1(3):6-
18. September 1973.
8. Smith, W.S., R.T. Shigehara, and W.F. Todd. A Method of
Interpreting Stack Sampling Data. Stack Sampling News. 1(2):8-17.
August 1973.
9. Standard Method for Sampling Stacks for Particulate Matter.
In: 1971 Annual Book of ASTM Standards, Part 23. ASTM Designation D
2928-71. Philadelphia, PA 1971.
10. Vennard, J.K. Elementary Fluid Mechanics. John Wiley and
Sons, Inc. New York. 1947.
11. Mitchell, W.J. and M.R. Midgett. Improved Procedure for
Determining Mercury Emissions from Mercury Cell Chlor-Alkali Plants.
J. APCA. 26:674-677. July 1976.
12. Shigehara, R.T. Adjustments in the EPA Nomograph for
Different Pitot Tube Coefficients and Dry Molecular Weights. Stack
Sampling News. 2:4-11. October 1974.
13. Vollaro, R.F. Recommended Procedure for Sample Traverses in
Ducts Smaller than 12 Inches in Diameter. U.S. Environmental
Protection Agency, Emission Measurement Branch. Research Triangle
Park, NC. November 1976.
14. Klein, R. and C. Hach. Standard Additions: Uses and
Limitation in Spectrophotometric Measurements. Amer. Lab. 9:21.
1977.
15. Perkin Elmer Corporation. Analytical Methods for Atomic
Absorption Spectrophotometry. Norwalk, Connecticut. September 1976.
BILLING CODE 6560-50-P

[[Page 62167]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.493

[[Page 62168]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.494

[[Page 62169]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.495

[[Page 62170]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.496

[[Page 62171]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.497

[[Page 62172]]

Method 101A--Determination of Particulate and Gaseous Mercury
Emissions From Sewage Sludge Incinerators

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 methods in Appendix A to 40 CFR Part
60 and 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: Methods 1, Method 2, Method
3, and Method 5 of Part 60 (Appendix A), and Method 101 Part 61
(Appendix B).

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Mercury (Hg)................... 7439-97-6 Dependent upon
spectrophotometer and
recorder.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of Hg emissions from sewage sludge incinerators and other sources as
specified in an applicable subpart of the regulations.
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 and gaseous Hg emissions are withdrawn
isokinetically from the source and are collected in acidic potassium
permanganate (KMnO4) solution. The Hg collected (in the
mercuric form) is reduced to elemental Hg, which is then aerated from
the solution into an optical cell and measured by atomic absorption
spectrophotometry.

3.0 Definitions. [Reserved]

4.0 Interferences

4.1 Sample Collection. Excessive oxidizable organic matter in the
stack gas prematurely depletes the KMnO4 solution and
thereby prevents further collection of Hg.
4.2 Analysis. Condensation of water vapor on the optical cell
windows causes a positive interference.

5.0 Safety

5.1 Disclaimer. This method may involve hazardous materials,
operations, and equipment. This test method may not address all of the
safety problems associated with its use. It is the responsibility of
the user of this test method to establish appropriate safety and health
practices and determine the applicability of regulatory limitations
prior to performing this test method.
5.2 Corrosive Reagents. The following reagents are hazardous.
Personal protective equipment and safe procedures are useful in
preventing chemical splashes. If contact occurs, immediately flush with
copious amounts of water for at least 15 minutes. Remove clothing under
shower and decontaminate. Treat residual chemical burns as thermal
burns.
5.2.1 Hydrochloric Acid (HCl). Highly toxic. 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.
5.2.2 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.
5.2.3 Sulfuric acid (H2SO4). Rapidly
destructive to body tissue. Will cause third degree burns. Eye damage
may result in blindness. Inhalation may be fatal from spasm of the
larynx, usually within 30 minutes. May cause lung tissue damage with
edema. 3 mg/m\3\ will cause lung damage in uninitiated. 1 mg/m\3\ for 8
hours will cause lung damage or, in higher concentrations, death.
Provide ventilation to limit inhalation. Reacts violently with metals
and organics.
5.3 Chlorine Evolution. Hydrochloric acid reacts with
KMnO4 to liberate chlorine gas. Although this is a minimal
concern when small quantities of HCl (5-10 ml) are used in the impinger
rinse, a potential safety hazard may still exist. At sources that emit
higher concentrations of oxidizable materials (e.g., power plants),
more HCl may be required to remove the larger amounts of brown deposit
formed in the impingers. In such cases, the potential safety hazards
due to sample container pressurization are greater, because of the
larger volume of HCl rinse added to the recovered sample. These hazards
are eliminated by storing and analyzing the HCl impinger wash
separately from the permanganate impinger sample.

6.0 Equipment and Supplies

6.1 Sample Collection and Sample Recovery. Same as Method 101,
Sections 6.1 and 6.2, respectively, with the following exceptions:
6.1.1 Probe Liner. Same as in Method 101, Section 6.1.2, except
that if a filter is used ahead of the impingers, the probe heating
system must be used to minimize the condensation of gaseous Hg.
6.1.2 Filter Holder (Optional). Borosilicate glass with a rigid
stainless-steel wire-screen filter support (do not use glass frit
supports) and a silicone rubber or Teflon gasket, designed to provide a
positive seal against leakage from outside or around the filter. The
filter holder must be equipped with a filter heating system capable of
maintaining a temperature around the filter holder of 120
14 deg.C (248 25 deg.F) during sampling to minimize both
water and gaseous Hg condensation. A filter may also be used in cases
where the stream contains large quantities of particulate matter.
6.2 Sample Analysis. Same as Method 101, Section 6.3, with the
following additions and exceptions:
6.2.1 Volumetric Pipets. Class A; 1-, 2-, 3-, 4-, 5-, 10-, and 20-
ml.
6.2.2 Graduated Cylinder. 25-ml.
6.2.3 Steam Bath.
6.2.4 Atomic Absorption Spectrophotometer or Equivalent. Any
atomic absorption unit with an open sample presentation area in which
to mount the optical cell is suitable. Instrument settings recommended
by the particular manufacturer should be followed. Instruments designed
specifically for the measurement of mercury using the cold-vapor
technique are commercially available and may be substituted for the
atomic absorption spectrophotometer.
6.2.5 Optical Cell. Alternatively, a heat lamp mounted above the
cell or a moisture trap installed upstream of the cell may be used.
6.2.6 Aeration Cell. Alternatively, aeration cells available with
commercial cold vapor instrumentation may be used.
6.2.7 Aeration Gas Cylinder. Nitrogen, argon, or dry, Hg-free air,
equipped with a single-stage regulator. Alternatively, aeration may be
provided

[[Page 62173]]

by a peristaltic metering pump. If a commercial cold vapor instrument
is used, follow the manufacturer's recommendations.

7.0 Reagents and Standards

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.
7.1 Sample Collection and Recovery. The following reagents are
required for sample collection and recovery:
7.1.1 Water. Deionized distilled, to conform to ASTM D 1193-77 or
91 Type 1. If high concentrations of organic matter are not expected to
be present, the analyst may eliminate the KMnO4 test for
oxidizable organic matter. Use this water in all dilutions and solution
preparations.
7.1.2 Nitric Acid, 50 Percent (V/V). Mix equal volumes of
concentrated HNO3 and water, being careful to add the acid
to the water slowly.
7.1.3 Silica Gel. Indicating type, 6 to 16 mesh. If previously
used, dry at 175 deg.C (350 deg.F) for 2 hours. New silica gel may be
used as received.
7.1.4 Filter (Optional). Glass fiber filter, without organic
binder, exhibiting at least 99.95 percent efficiency on 0.3-m
dioctyl phthalate smoke particles. The filter in cases where the gas
stream contains large quantities of particulate matter, but blank
filters should be analyzed for Hg content.
7.1.5 Sulfuric Acid, 10 Percent (V/V). Carefully add and mix 100
ml of concentrated H2SO4 to 900 ml of water.
7.1.6 Absorbing Solution, 4 Percent KMnO4 (W/V).
Prepare fresh daily. Dissolve 40 g of KMnO4 in sufficient 10
percent H2SO4 to make 1 liter. Prepare and store
in glass bottles to prevent degradation.
7.1.7 Hydrochloric Acid, 8 N. Carefully add and mix 67 ml of
concentrated HCl to 33 ml of water.
7.2 Sample Analysis. The following reagents and standards are
required for sample analysis:
7.2.1 Water. Same as in Section 7.1.1.
7.2.2 Tin (II) Solution. Prepare fresh daily, and keep sealed when
not being used. Completely dissolve 20 g of tin (II) chloride (or 25 g
of tin (II) sulfate) crystals (Baker Analyzed reagent grade or any
other brand that will give a clear solution) in 25 ml of concentrated
HCl. Dilute to 250 ml with water. Do not substitute HNO3,
H2SO4, or other strong acids for the HCl.
7.2.3 Sodium Chloride-Hydroxylamine Solution. Dissolve 12 g of
sodium chloride and 12 g of hydroxylamine sulfate (or 12 g of
hydroxylamine hydrochloride) in water and dilute to 100 ml.
7.2.4 Hydrochloric Acid, 8 N. Same as Section 7.1.7.
7.2.5 Nitric Acid, 15 Percent (V/V). Carefully add 15 ml
HNO3 to 85 ml of water.
7.2.6 Antifoam B Silicon Emulsion. J.T. Baker Company (or
equivalent).
7.2.7 Mercury Stock Solution, 1 mg Hg/ml. Prepare and store all Hg
standard solutions in borosilicate glass containers. Completely
dissolve 0.1354 g of Hg (II) chloride in 75 ml of water. Add 10 ml of
concentrated HNO3, and adjust the volume to exactly 100 ml
with water. Mix thoroughly. This solution is stable for at least one
month.
7.2.8 Intermediate Hg Standard Solution, 10 g/ml. Prepare
fresh weekly. Pipet 5.0 ml of the Hg stock solution (Section 7.2.7)
into a 500 ml volumetric flask, and add 20 ml of 15 percent
HNO3 solution. Adjust the volume to exactly 500 ml with
water. Thoroughly mix the solution.
7.2.9 Working Hg Standard Solution, 200 ng Hg/ml. Prepare fresh
daily. Pipet 5.0 ml from the ``Intermediate Hg Standard Solution''
(Section 7.2.8) into a 250-ml volumetric flask. Add 5 ml of 4 percent
KMnO4 absorbing solution and 5 ml of 15 percent
HNO3. Adjust the volume to exactly 250 ml with water. Mix
thoroughly.
7.2.10 Potassium Permanganate, 5 Percent (W/V). Dissolve 5 g of
KMnO4 in water and dilute to 100 ml.
7.2.11 Filter. Whatman No. 40, or equivalent.

8.0 Sample Collection, Preservation, Transport, and Storage

Same as Method 101, Section 8.0, with the exception of the
following:
8.1 Preliminary Determinations. Same as Method 101, Section 8.2,
except that the liberation of free iodine in the first impinger due to
high Hg or sulfur dioxide concentrations is not applicable. In this
method, high oxidizable organic content may make it impossible to
sample for the desired minimum time. This problem is indicated by the
complete bleaching of the purple color of the KMnO4
solution. In cases where an excess of water condensation is
encountered, collect two runs to make one sample, or add an extra
impinger in front of the first impinger (also containing acidified
KMnO4 solution).
8.2 Preparation of Sampling Train. Same as Method 101, Section
8.3, with the exception of the following:
8.2.1 In this method, clean all the glass components by rinsing
with 50 percent HNO3, tap water, 8 N HCl, tap water, and
finally with deionized distilled water. Then place 50 ml of absorbing
solution in the first impinger and 100 ml in each of the second and
third impingers.
8.2.2 If a filter is used, use a pair of tweezers to place the
filter in the filter holder. Be sure to center the filter, and place
the gasket in the proper position to prevent the sample gas stream from
bypassing the filter. Check the filter for tears after assembly is
completed. Be sure also to set the filter heating system at the desired
operating temperature after the sampling train has been assembled.
8.3 Sampling Train Operation. In addition to the procedure
outlined in Method 101, Section 8.5, maintain a temperature around the
filter (if applicable) of 120 14 deg.C (248
25 deg.F).
8.4 Sample Recovery. Same as Method 101, Section 8.7, with the
exception of the following:
8.4.1 Transfer the probe, impinger assembly, and (if applicable)
filter assembly to the cleanup area.
8.4.2 Treat the sample as follows:
8.4.2.1 Container No. 1 (Impinger, Probe, and Filter Holder) and,
if applicable, Container No. 1A (HCl rinse).
8.4.2.1.1 Using a graduated cylinder, measure the liquid in the
first three impingers to within 1 ml. Record the volume of liquid
present (e.g., see Figure 5-6 of Method 5). This information is needed
to calculate the moisture content of the effluent gas. (Use only
graduated cylinder and glass storage bottles that have been precleaned
as in Section 8.2.1.) Place the contents of the first three impingers
(four if an extra impinger was added as described in Section 8.1) into
a 1000-ml glass sample bottle labeled Container No. 1.

Note: If a filter is used, remove the filter from its holder as
outlined under Section 8.4.3.

8.4.2.1.2 Taking care that dust on the outside of the probe or
other exterior surfaces does not get into the sample, quantitatively
recover the Hg (and any condensate) from the probe nozzle, probe
fitting, probe liner, front half of the filter holder (if applicable),
and impingers as follows: Rinse these components with a total of 400 ml
(350 ml if an extra impinger was added as described in Section 8.1) of
fresh absorbing solution, carefully assuring removal of all loose
particulate matter from the impingers; add all washings to the 1000 ml
glass sample bottle. To remove any residual brown deposits on the
glassware following the

[[Page 62174]]

permanganate rinse, rinse with approximately 100 ml of water, carefully
assuring removal of all loose particulate matter from the impingers.
Add this rinse to Container No. 1.
8.4.2.1.3 If no visible deposits remain after this water rinse, do
not rinse with 8 N HCl. If deposits do remain on the glassware after
the water rinse, wash impinger walls and stems with 25 ml of 8 N HCl,
and place the wash in a separate container labeled Container No. 1A as
follows: Place 200 ml of water in a sample container labeled Container
No. 1A. Wash the impinger walls and stem with the HCl by turning the
impinger on its side and rotating it so that the HCl contacts all
inside surfaces. Pour the HCl wash carefully with stirring into
Container No. 1A.
8.4.2.1.4 After all washings have been collected in the
appropriate sample container(s), tighten the lid(s) on the container(s)
to prevent leakage during shipment to the laboratory. Mark the height
of the fluid level to allow subsequent determination of whether leakage
has occurred during transport. Label each container to identify its
contents clearly.
8.4.3 Container No. 2 (Silica Gel). Same as Method 5, Section
8.7.6.3.
8.4.4 Container No. 3 (Filter). If a filter was used, carefully
remove it from the filter holder, place it in a 100-ml glass sample
bottle, and add 20 to 40 ml of absorbing solution. If it is necessary
to fold the filter, be sure that the particulate cake is inside the
fold. Carefully transfer to the 100-ml sample bottle any particulate
matter and filter fibers that adhere to the filter holder gasket by
using a dry Nylon bristle brush and a sharp-edged blade. Seal the
container. Label the container to identify its contents clearly. Mark
the height of the fluid level to allow subsequent determination of
whether leakage has occurred during transport.
8.4.5 Container No. 4 (Filter Blank). If a filter was used, treat
an unused filter from the same filter lot as that used for sampling
according to the procedures outlined in Section 8.4.4.
8.4.6 Container No. 5 (Absorbing Solution Blank). Place 650 ml of
4 percent KMnO4 absorbing solution in a 1000-ml sample
bottle. Seal the container.
8.4.7 Container No. 6 (HCl Rinse Blank). Place 200 ml of water in
a 1000-ml sample bottle, and add 25 ml of 8 N HCl carefully with
stirring. Seal the container. Only one blank sample per 3 runs is
required.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.0, 10.0..................... Sampling Ensure accuracy and
equipment leak- precision of
checks and sampling
calibration. measurements.
10.2.......................... Spectrophotometer Ensure linearity of
calibration. spectrophotometer
response to
standards.
11.3.3........................ Check for matrix Eliminate matrix
effects. effects.
------------------------------------------------------------------------

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

10.0 Calibration and Standardization

Same as Method 101, Section 10.0, with the following exceptions:
10.1 Optical Cell Heating System Calibration. Same as in Method
101, Section 10.4, except use a-25 ml graduated cylinder to add 25 ml
of water to the bottle section of the aeration cell.
10.2 Spectrophotometer and Recorder Calibration.
10.2.1 The Hg response may be measured by either peak height or
peak area.

Note: The temperature of the solution affects the rate at which
elemental Hg is released from a solution and, consequently, it
affects the shape of the absorption curve (area) and the point of
maximum absorbance (peak height). To obtain reproducible results,
all solutions must be brought to room temperature before use.

10.2.2 Set the spectrophotometer wave length at 253.7 nm, and make
certain the optical cell is at the minimum temperature that will
prevent water condensation. Then set the recorder scale as follows:
Using a 25-ml graduated cylinder, add 25 ml of water to the aeration
cell bottle. Add three drops of Antifoam B to the bottle, and then
pipet 5.0 ml of the working Hg standard solution into the aeration
cell.

Note: Always add the Hg-containing solution to the aeration cell
after the 25 ml of water.

10.2.3 Place a Teflon-coated stirring bar in the bottle. Add 5 ml
of absorbing solution to the aeration bottle, and mix well. Before
attaching the bottle section to the bubbler section of the aeration
cell, make certain that (1) the aeration cell exit arm stopcock (Figure
101-3 of Method 101) is closed (so that Hg will not prematurely enter
the optical cell when the reducing agent is being added) and (2) there
is no flow through the bubbler. If conditions (1) and (2) are met,
attach the bottle section to the bubbler section of the aeration cell.
Add sodium chloride-hydroxylamine in 1 ml increments until the solution
is colorless. Now add 5 ml of tin (II) solution to the aeration bottle
through the side arm, and immediately stopper the side arm. Stir the
solution for 15 seconds, turn on the recorder, open the aeration cell
exit arm stopcock, and immediately initiate aeration with continued
stirring. Determine the maximum absorbance of the standard, and set
this value to read 90 percent of the recorder full scale.

11.0 Analytical Procedure

11.1 Sample Loss Check. Check the liquid level in each container
to see if liquid was lost during transport. If a noticeable amount of
leakage occurred, either void the sample or use methods subject to the
approval of the Administrator to account for the losses.
11.2 Sample Preparation. Treat sample containers as follows:
11.2.1 Containers No. 3 and No. 4 (Filter and Filter Blank).
11.2.1.1 If a filter is used, place the contents, including the
filter, of Containers No. 3 and No. 4 in separate 250-ml beakers, and
heat the beakers on a steam bath until most of the liquid has
evaporated. Do not heat to dryness. Add 20 ml of concentrated
HNO3 to the beakers, cover them with a watch glass, and heat
on a hot plate at 70 deg.C (160 deg.F) for 2 hours. Remove from the
hot plate.
11.2.1.2 Filter the solution from digestion of the Container No. 3
contents through Whatman No. 40 filter paper, and save the filtrate for
addition to the Container No. 1 filtrate as described in Section
11.2.2. Discard the filter paper.
11.2.1.3 Filter the solution from digestion of the Container No. 4
contents through Whatman No. 40 filter paper, and save the filtrate for
addition to Container No. 5 filtrate as described in Section 11.2.3
below. Discard the filter paper.
11.2.2 Container No. 1 (Impingers, Probe, and Filter Holder) and,
if applicable, No. 1A (HCl rinse).
11.2.2.1 Filter the contents of Container No. 1 through Whatman
No. 40 filter paper into a 1 liter volumetric flask to remove the brown
manganese

[[Page 62175]]

dioxide (MnO2) precipitate. Save the filter for digestion of
the brown MnO2 precipitate. Add the sample filtrate from
Container No. 3 to the 1-liter volumetric flask, and dilute to volume
with water. If the combined filtrates are greater than 1000 ml,
determine the volume to the nearest ml and make the appropriate
corrections for blank subtractions. Mix thoroughly. Mark the filtrate
as analysis Sample No. A.1 and analyze for Hg within 48 hr of the
filtration step. Place the saved filter, which was used to remove the
brown MnO2 precipitate, into an appropriate sized container.
In a laboratory hood, add 25 ml of 8 N HCl to the filter and allow to
digest for a minimum of 24 hours at room temperature.
11.2.2.2 Filter the contents of Container 1A through Whatman No.
40 filter paper into a 500-ml volumetric flask. Then filter the
digestate of the brown MnO2 precipitate from Container No. 1
through Whatman No. 40 filter paper into the same 500-ml volumetric
flask, and dilute to volume with water. Mark this combined 500 ml
dilute solution as analysis Sample No. A.2. Discard the filters.
11.2.3 Container No. 5 (Absorbing Solution Blank) and No. 6 (HCl
Rinse Blank).
11.2.3.1 Treat Container No. 5 as Container No. 1 (as described in
Section 11.2.2), except substitute the filter blank filtrate from
Container No. 4 for the sample filtrate from Container No. 3, and mark
as Sample A.1 Blank.
11.2.3.2 Treat Container No. 6 as Container No. 1A, (as described
in Section 11.2.2, except substitute the filtrate from the digested
blank MnO2 precipitate for the filtrate from the digested
sample MnO2 precipitate, and mark as Sample No. A.2 Blank.

Note: When analyzing samples A.1 Blank and HCl A.2 Blank, always
begin with 10 ml aliquots. This applies specifically to blank
samples.

11.3 Analysis. Calibrate the analytical equipment and develop a
calibration curve as outlined in Section 10.0.
11.3.1 Mercury Samples. Then repeat the procedure used to
establish the calibration curve with appropriately sized aliquots (1 to
10 ml) of the samples (from Sections 11.2.2 and 11.2.3) until two
consecutive peak heights agree within 3 percent of their average value.
If the 10 ml sample is below the detectable limit, use a larger aliquot
(up to 20 ml), but decrease the volume of water added to the aeration
cell accordingly to prevent the solution volume from exceeding the
capacity of the aeration bottle. If the peak maximum of a 1.0 ml
aliquot is off scale, further dilute the original sample to bring the
Hg concentration into the calibration range of the spectrophotometer.
If the Hg content of the absorbing solution and filter blank is below
the working range of the analytical method, use zero for the blank.
11.3.2 Run a blank and standard at least after every five samples
to check the spectrophotometer calibration; recalibrate as necessary.
11.3.3 Check for Matrix Effects (optional). Same as Method 101,
Section 11.3.3.

12.0 Data Analysis and Calculations

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

12.1 Nomenclature.

C(fltr)Hg = Total ng of Hg in aliquot of KMnO4
filtrate and HNO3 digestion of filter analyzed (aliquot of
analysis Sample No. A.1).
C(fltr blk)Hg = Total ng of Hg in aliquot of
KMnO4 blank and HNO3 digestion of blank filter
analyzed (aliquot of analysis Sample No. A.1 blank).
C(HC1 blk)Hg = Total ng of Hg analyzed in aliquot of the
500-ml analysis Sample No. HCl A.2 blank.
C(HCl)Hg = Total ng of Hg analyzed in the aliquot from the
500-ml analysis Sample No. HCl A.2.
DF = Dilution factor for the HCl-digested Hg-containing solution,
Analysis Sample No. ``HCl A.2.''
DFblk = Dilution factor for the HCl-digested Hg containing
solution, Analysis Sample No. ``HCl A.2 blank.'' (Refer to sample No.
``HCl A.2'' dilution factor above.)
m(fltr)Hg = Total blank corrected g of Hg in
KMnO4 filtrate and HNO3 digestion of filter
sample.
m(HCl)Hg = Total blank corrected g of Hg in HCl
rinse and HCl digestate of filter sample.
mHg = Total blank corrected Hg content in each sample,
g.
S = Aliquot volume of sample added to aeration cell, ml.
Sblk = Aliquot volume of blank added to aeration cell, ml.
Vf(blk) = Solution volume of blank sample, 1000 ml for
samples diluted as described in Section 11.2.2.
Vf(fltr) = Solution volume of original sample, normally 1000
ml for samples diluted as described in Section 11.2.2.
Vf(HCl) = Solution volume of original sample, 500 ml for
samples diluted as described in Section 11.2.1.
10-\3\ = Conversion factor, g/ng.

12.2 Average Dry Gas Meter Temperature and Average Orifice
Pressure Drop, Dry Gas Volume, Volume of Water Vapor Condensed,
Moisture Content, Isokinetic Variation, and Stack Gas Velocity and
Volumetric Flow Rate. Same as Method 5, Sections 12.2 through 12.5,
12.11, and 12.12, respectively.
12.3 Total Mercury.
12.3.1 For each source sample, correct the average maximum
absorbance of the two consecutive samples whose peak heights agree
within 3 percent of their average for the contribution of the blank.
Use the calibration curve and these corrected averages to determine the
final total weight of Hg in ng in the aeration cell for each source
sample.
12.3.2 Correct for any dilutions made to bring the sample into the
working range of the spectrophotometer.
[GRAPHIC] [TIFF OMITTED] TR17OC00.498

Note: This dilution factor applies only to the intermediate
dilution steps, since the original sample volume
[(Vf)HCL] of ``HCl A.2'' has been factored out
in the equation along with the sample aliquot (S). In Eq. 101A-1,
the sample aliquot, S, is introduced directly into the aeration cell
for analysis according to the procedure outlined in Section 11.3.1.
A dilution factor is required only if it is necessary to bring the
sample into the analytical instrument's calibration range.

Note: The maximum allowable blank subtraction for the HCl is the
lesser of the two following values: (1) the actual blank measured
value (analysis Sample No. HCl A.2 blank), or (2) 5% of the Hg
content in the combined HCl rinse and digested sample (analysis
Sample No. HCl A.2).

[[Page 62176]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.499

Note: The maximum allowable blank subtraction for the HCl is the
lesser of the two following values: (1) the actual blank measured
value (analysis Sample No. ``A.1 blank''), or (2) 5% of the Hg
content in the filtrate (analysis Sample No. ``A.1'').

[GRAPHIC] [TIFF OMITTED] TR17OC00.500

12.3 Mercury Emission Rate. Same as Method 101, Section 12.3.
12.4 Determination of Compliance. Same as Method 101, Section
12.4.

13.0 Method Performance

13.1 Precision. Based on eight paired-train tests, the intra-
laboratory standard deviation was estimated to be 4.8 g/ml in
the concentration range of 50 to 130 g/m3.
13.2 Bias. [Reserved]
13.3 Range. After initial dilution, the range of this method is 20
to 800 ng Hg/ml. The upper limit can be extended by further dilution of
the sample.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as Section 16.0 of Method 101, with the addition of the
following:

1. Mitchell, W.J., et al. Test Methods to Determine the Mercury
Emissions from Sludge Incineration Plants. U.S. Environmental
Protection Agency. Research Triangle Park, NC. Publication No. EPA-
600/4-79-058. September 1979.
2. Wilshire, Frank W., et al. Reliability Study of the U.S.
EPA's Method 101A--Determination of Particulate and Gaseous Mercury
Emissions. U.S. Environmental Protection Agency. Research Triangle
Park, NC. Report No. 600/D-31/219 AREAL 367, NTIS Acc No. PB91-
233361.
3. Memorandum from William J. Mitchell to Roger T. Shigehara
discussing the potential safety hazard in Section 7.2 of Method
101A. February 28, 1990.

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

Method 102--Determination of Particulate and Gaseous Mercury
Emissions From Chlor-Alkali Plants (Hydrogen Streams)

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 and in
Appendix A to 40 CFR Part 60. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at
least the following additional test methods: Method 1, Method 2,
Method 3, Method 5, and Method 101.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Mercury (Hg)................... 7439-97-6 Dependent upon recorder
and spectrophotometer.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of Hg emissions, including both particulate and gaseous Hg, from chlor-
alkali plants and other sources (as specified in the regulations) where
the carrier-gas stream in the duct or stack is principally hydrogen.
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 and gaseous Hg emissions are withdrawn
isokinetically from the source and collected in acidic iodine
monochloride (ICl) solution. The Hg collected (in the mercuric form) is
reduced to elemental Hg, which is then aerated from the solution into
an optical cell and measured by atomic absorption spectrophotometry.

3.0 Definitions [Reserved]

4.0 Interferences

Same as Method 101, Section 4.2.

5.0 Safety

Note: A smaller ID tubing may cause the orifice meter
calibration to be erroneous. Take care to ensure that the exhaust
line is not bent or pinched.

6.0 Equipment and Supplies

Same as Method 101, Section 6.0, with the exception of the
following:
6.1 Probe Heating System. Do not use, unless otherwise specified.
6.2 Glass Fiber Filter. Do not use, unless otherwise specified.

7.0 Reagents and Standards

Same as Method 101, Section 7.0.

[[Page 62177]]

8.0 Sample Collection, Preservation, Transport, and Storage

Same as Method 101, Section 8.0, with the exception of the
following:
8.1 Setting of Isokinetic Rates.
8.1.1 If a nomograph is used, take special care in the calculation
of the molecular weight of the stack gas and in the setting of the
nomograph to maintain isokinetic conditions during sampling (Sections
8.1.1.1 through 8.1.1.3 below).
8.1.1.1 Calibrate the meter box orifice. Use the techniques
described in APTD-0576 (see Reference 9 in Section 17.0 of Method 5).
Calibration of the orifice meter at flow conditions that simulate the
conditions at the source is suggested. Calibration should either be
done with hydrogen or with some other gas having similar Reynolds
Number so that there is similarity between the Reynolds Numbers during
calibration and during sampling.
8.1.1.2 The nomograph described in APTD-0576 cannot be used to
calculate the C factor because the nomograph is designed for use when
the stack gas dry molecular weight is 29 4. Instead, the
following calculation should be made to determine the proper C factor:
[GRAPHIC] [TIFF OMITTED] TR17OC00.501

Where:

Bws = Fraction by volume of water vapor in the stack gas.
Cp = Pitot tube calibration coefficient, dimensionless.
Md = Dry molecular weight of stack gas, lb/lb-mole.
Ps = Absolute pressure of stack gas, in. Hg.
Pm = Absolute pressure of gas at the meter, in. Hg.
Tm = Absolute temperature of gas at the orifice, deg.R.
H@ = Meter box calibration factor obtained in
Section 8.1.1.1, in. H2O.
0.00154 = (in. H2O/ deg.R).

Note: This calculation is left in English units, and is not
converted to metric units because nomographs are based on English
units.

8.1.1.3 Set the calculated C factor on the operating nomograph,
and select the proper nozzle diameter and K factor as specified in
APTD-0576. If the C factor obtained in Section 8.1.1.2 exceeds the
values specified on the existing operating nomograph, expand the C
scale logarithmically so that the values can be properly located.
8.1.2 If a calculator is used to set isokinetic rates, it is
suggested that the isokinetic equation presented in Reference 13 in
Section 17.0 of Method 101 be consulted.
8.2 Sampling in Small (12-in. Diameter) Stacks. When the stack
diameter (or equivalent diameter) is less than 12 inches, conventional
pitot tube-probe assemblies should not be used. For sampling
guidelines, see Reference 14 in Section 17.0 of Method 101.

9.0 Quality Control

Same as Method 101, Section 9.0.

10.0 Calibration and Standardizations

Same as Method 101, Section 10.0.

11.0 Analytical Procedure

Same as Method 101, Section 11.0.

12.0 Data Analysis and Calculations

Same as Method 101, Section 12.0.

13.0 Method Performance

Same as Method 101, Section 13.0.
13.1 Analytical Range. After initial dilution, the range of this
method is 0.5 to 120 g Hg/ml. The upper limit can be extended
by further dilution of the sample.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

Same as Method 101, Section 16.0.

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

Method 103--Beryllium Screening Method

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Beryllium (Be)................. 7440-41-7 Dependent upon
analytical procedure
used.
------------------------------------------------------------------------

1.2 Applicability. This procedure details guidelines and
requirements for methods acceptable for use in determining Be emissions
in ducts or stacks at stationary sources.
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 Be emissions are withdrawn isokinetically from
three points in a duct or stack and are collected on a filter. The
collected sample is analyzed for Be using an appropriate technique.

3.0 Definitions. [Reserved]

4.0 Interferences. [Reserved]

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. A schematic of the required sampling train
configuration is shown in Figure 103-1 in Section 17.0. The essential
components of the train are as follows:

[[Page 62178]]

6.1.1 Nozzle. Stainless steel, or equivalent, with sharp, tapered
leading edge.
6.1.2 Probe. Sheathed borosilicate or quartz glass tubing.
6.1.3 Filter. Millipore AA, or equivalent, with appropriate filter
holder that provides a positive seal against leakage from outside or
around the filter. It is suggested that a Whatman 41, or equivalent, be
placed immediately against the back side of the Millipore filter as a
guard against breakage of the Millipore. Include the backup filter in
the analysis. To be equivalent, other filters shall exhibit at least
99.95 percent efficiency (0.05 percent penetration) on 0.3 micron
dioctyl phthalate smoke particles, and be amenable to the Be analysis
procedure. The filter efficiency tests shall be conducted in accordance
with ASTM D 2986-71, 78, 95a (incorporated by reference--see
Sec. 61.18). Test data from the supplier's quality control program are
sufficient for this purpose.
6.1.4 Meter-Pump System. Any system that will maintain isokinetic
sampling rate, determine sample volume, and is capable of a sampling
rate of greater than 14 lpm (0.5 cfm).
6.2 Measurement of Stack Conditions. The following equipment is
used to measure stack conditions:
6.2.1 Pitot Tube. Type S, or equivalent, with a constant
coefficient (5 percent) over the working range.
6.2.2 Inclined Manometer, or Equivalent. To measure velocity head
to 10 percent of the minimum value.
6.2.3 Temperature Measuring Device. To measure stack temperature
to 1.5 percent of the minimum absolute stack temperature.
6.2.4 Pressure Measuring Device. To measure stack pressure to
2.5 mm Hg (0.1 in. Hg).
6.2.5 Barometer. To measure atmospheric pressure to
2.5 mm Hg (0.1 in. Hg).
6.2.6 Wet and Dry Bulb Thermometers, Drying Tubes, Condensers, or
Equivalent. To determine stack gas moisture content to 1
percent.
6.3 Sample Recovery.
6.3.1 Probe Cleaning Equipment. Probe brush or cleaning rod at
least as long as probe, or equivalent. Clean cotton balls, or
equivalent, should be used with the rod.
6.3.2 Leakless Glass Sample Bottles. To contain sample.
6.4 Analysis. All equipment necessary to perform an atomic
absorption, spectrographic, fluorometric, chromatographic, or
equivalent analysis.

7.0 Reagents and Standards

7.1 Sample Recovery.
7.1.1 Water. Deionized distilled, to conform to ASTM D 1193-77, 91
(incorporated by reference--see Sec. 61.18), Type 3.
7.1.2 Acetone. Reagent grade.
7.1.3 Wash Acid, 50 Percent (V/V) Hydrochloric Acid (HCl). Mix
equal volumes of concentrated HCl and water, being careful to add the
acid slowly to the water.
7.2 Analysis. Reagents and standards as necessary for the selected
analytical procedure.

8.0 Sample Collection, Preservation, Transport, and Storage

Guidelines for source testing are detailed in the following
sections. These guidelines are generally applicable; however, most
sample sites differ to some degree and temporary alterations such as
stack extensions or expansions often are required to insure the best
possible sample site. Further, since Be is hazardous, care should be
taken to minimize exposure. Finally, since the total quantity of Be to
be collected is quite small, the test must be carefully conducted to
prevent contamination or loss of sample.
8.1 Selection of a Sampling Site and Number of Sample Runs. Select
a suitable sample site that is as close as practicable to the point of
atmospheric emission. If possible, stacks smaller than one foot in
diameter should not be sampled.
8.1.1 Ideal Sampling Site. The ideal sampling site is at least
eight stack or duct diameters downstream and two diameters upstream
from any flow disturbance such as a bend, expansion or contraction. For
rectangular cross sections, use Equation 103-1 in Section 12.2 to
determine an equivalent diameter, De.
8.1.2 Alternate Sampling Site. Some sampling situations may render
the above sampling site criteria impractical. In such cases, select an
alternate site no less than two diameters downstream and one-half
diameter upstream from any point of flow disturbance. Additional sample
runs are recommended at any sample site not meeting the criteria of
Section 8.1.1.
8.1.3 Number of Sample Runs Per Test. Three sample runs constitute
a test. Conduct each run at one of three different points. Select three
points that proportionately divide the diameter, or are located at 25,
50, and 75 percent of the diameter from the inside wall. For horizontal
ducts, sample on a vertical line through the centroid. For rectangular
ducts, sample on a line through the centroid and parallel to a side. If
additional sample runs are performed per Section 8.1.2, proportionately
divide the duct to accommodate the total number of runs.
8.2 Measurement of Stack Conditions. Using the equipment described
in Section 6.2, measure the stack gas pressure, moisture, and
temperature to determine the molecular weight of the stack gas. Sound
engineering estimates may be made in lieu of direct measurements.
Describe the basis for such estimates in the test report.
8.3 Preparation of Sampling Train.
8.3.1 Assemble the sampling train as shown in Figure 103-1. It is
recommended that all glassware be precleaned by soaking in wash acid
for two hours.
8.3.2 Leak check the sampling train at the sampling site. The
leakage rate should not be in excess of 1 percent of the desired sample
rate.
8.4 Sampling Train Operation.
8.4.1 For each run, measure the velocity at the selected sampling
point. Determine the isokinetic sampling rate. Record the velocity head
and the required sampling rate. Place the nozzle at the sampling point
with the tip pointing directly into the gas stream. Immediately start
the pump and adjust the flow to isokinetic conditions. At the
conclusion of the test, record the sampling rate. Again measure the
velocity head at the sampling point. The required isokinetic rate at
the end of the period should not have deviated more than 20 percent
from that originally calculated. Describe the reason for any deviation
beyond 20 percent in the test report.
8.4.2 Sample at a minimum rate of 14 liters/min (0.5 cfm). Obtain
samples over such a period or periods of time as are necessary to
determine the maximum emissions which would occur in a 24-hour period.
In the case of cyclic operations, perform sufficient sample runs so as
to allow determination or calculation of the emissions that occur over
the duration of the cycle. A minimum sampling time of two hours per run
is recommended.
8.5 Sample Recovery.
8.5.1 It is recommended that all glassware be precleaned as in
Section 8.3. Sample recovery should also be performed in an area free
of possible Be contamination. When the sampling train is moved,
exercise care to prevent breakage and contamination. Set aside a
portion of the acetone used in the sample recovery as a blank for
analysis. The total amount of acetone used should be measured for
accurate blank correction. Blanks can be eliminated if

[[Page 62179]]

prior analysis shows negligible amounts.
8.5.2 Remove the filter (and backup filter, if used) and any loose
particulate matter from filter holder, and place in a container.
8.5.3 Clean the probe with acetone and a brush or long rod and
cotton balls. Wash into the container with the filter. Wash out the
filter holder with acetone, and add to the same container.

9.0 Quality Control. [Reserved]

10.0 Calibration and Standardization

10.1 Sampling Train. As a procedural check, compare the sampling
rate regulation with a dry gas meter, spirometer, rotameter (calibrated
for prevailing atmospheric conditions), or equivalent, attached to the
nozzle inlet of the complete sampling train.
10.2 Analysis. Perform the analysis standardization as suggested
by the manufacturer of the instrument, or the procedures for the
analytical method in use.

11.0 Analytical Procedure

Make the necessary preparation of samples and analyze for Be. Any
currently acceptable method (e.g., atomic absorption, spectrographic,
fluorometric, chromatographic) may be used.

12.0 Data Analysis and Calculations

12.1 Nomenclature.

As(avg) = Stack area, m\2\ (ft\2\).
L = Length.
R = Be emission rate, g/day.
Vs(avg) = Average stack gas velocity, m/sec (ft/sec).
Vtotal = Total volume of gas sampled, m\3\ (ft\3\).
W = Width.
Wt = Total weight of Be collected, mg.
10-6 = Conversion factor, g/g.
86,400 = Conversion factor, sec/day.

12.2 Calculate the equivalent diameter, De, for a rectangular
cross section as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.502

12.3 Calculate the Be emission rate, R, in g/day for each stack
using Equation 103-2. For cyclic operations, use only the time per day
each stack is in operation. The total Be emission rate from a source is
the summation of results from all stacks.
[GRAPHIC] [TIFF OMITTED] TR17OC00.503

12.4 Test Report. Prepare a test report that includes as a
minimum: A detailed description of the sampling train used, results of
the procedural check described in Section 10.1 with all data and
calculations made, all pertinent data taken during the test, the basis
for any estimates made, isokinetic sampling calculations, and emission
results. Include a description of the test site, with a block diagram
and brief description of the process, location of the sample points in
the stack cross section, and stack dimensions and distances from any
point of disturbance.

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References. [Reserved]

BILLING CODE 6560-50-P

[[Page 62180]]

17.0 Tables, Diagrams, Flow Charts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.504

BILLING CODE 6560-50-C

[[Page 62181]]

Method 104--Determination of Beryllium Emissions From Stationary
Sources

Note: This method does not include all of the specifications
(e.g., equipment and supplies) and procedures (e.g., sampling and
analytical) essential to its performance. Some material is
incorporated by reference from methods in Appendix A to 40 CFR part
60. Therefore, to obtain reliable results, persons using this method
should have a thorough knowledge of at least the following
additional test methods: Method 1, Method 2, Method 3, and Method 5
in Appendix A, Part 60.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Beryllium (Be)................. 7440-41-7 Dependent upon
recorder and
spectrophotometer.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of Be emissions in ducts or stacks at stationary sources. Unless
otherwise specified, this method is not intended to apply to gas
streams other than those emitted directly to the atmosphere without
further processing.
1.3 Data Quality Objectives. Adherences 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 and gaseous Be emissions are withdrawn
isokinetically from the source and are collected on a glass fiber
filter and in water. The collected sample is digested in an acid
solution and is analyzed by atomic absorption spectrophotometry.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Matrix Effects. Analysis for Be by flame atomic absorption
spectrophotometry is sensitive to the chemical composition and to the
physical properties (e.g., viscosity, pH) of the sample. Aluminum and
silicon in particular are known to interfere when present in
appreciable quantities. The analytical procedure includes (optionally)
the use of the Method of Standard Additions to check for these matrix
effects, and sample analysis using the Method of Standard Additions if
significant matrix effects are found to be present (see Reference 2 in
Section 16.0).

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. Same as Method 5, Section 6.1, with the
exception of the following:
6.1.1 Sampling Train. Same as Method 5, Section 6.1.1, with the
exception of the following:
6.1.2 Probe Liner. Borosilicate or quartz glass tubing. A heating
system capable of maintaining a gas temperature of 120 14
deg.C (248 25 deg.F) at the probe exit during sampling to
prevent water condensation may be used.

Note: Do not use metal probe liners.

6.1.3 Filter Holder. Borosilicate glass, with a glass frit filter
support and a silicone rubber gasket. Other materials of construction
(e.g., stainless steel, Teflon, Viton) may be used, subject to the
approval of the Administrator. The holder design shall provide a
positive seal against leakage from the outside or around the filter.
The holder shall be attached immediately at the outlet of the probe. A
heating system capable of maintaining the filter at a minimum
temperature in the range of the stack temperature may be used to
prevent condensation from occurring.
6.1.4 Impingers. Four Greenburg-Smith impingers connected in
series with leak-free ground glass fittings or any similar leak-free
noncontaminating fittings. For the first, third, and fourth impingers,
use impingers that are modified by replacing the tip with a 13 mm-ID
(0.5 in.) glass tube extending to 13 mm (0.5 in.) from the bottom of
the flask may be used.
6.2 Sample Recovery. The following items are needed for sample
recovery:
6.2.1 Probe Cleaning Rod. At least as long as probe.
6.2.2 Glass Sample Bottles. Leakless, with Teflon-lined caps, 1000
ml.
6.2.3 Petri Dishes. For filter samples, glass or polyethylene,
unless otherwise specified by the Administrator.
6.2.4 Graduated Cylinder. 250 ml.
6.2.5 Funnel and Rubber Policeman. To aid in transfer of silica
gel to container; not necessary if silica gel is weighed in the field.
6.2.6 Funnel. Glass, to aid in sample recovery.
6.2.7 Plastic Jar. Approximately 300 ml.
6.3 Analysis. The following items are needed for sample analysis:
6.3.1 Atomic Absorption Spectrophotometer. Perkin-Elmer 303, or
equivalent, with nitrous oxide/acetylene burner.
6.3.2 Hot Plate.
6.3.3 Perchloric Acid Fume Hood.

7.0 Reagents and Standards

Note: 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.

[[Page 62182]]

7.1 Sample Collection. Same as Method 5, Section 7.1, including
deionized distilled water conforming to ASTM D 1193-77 or 91
(incorporated by reference--see Sec. 61.18), Type 3. The Millipore AA
filter is recommended.
7.2 Sample Recovery. Same as Method 5 in Appendix A, Part 60,
Section 7.2, with the addition of the following:
7.2.1 Wash Acid, 50 Percent (V/V) Hydrochloric Acid (HCl). Mix
equal volumes of concentrated HCl and water, being careful to add the
acid slowly to the water.
7.3 Sample Preparation and Analysis. The following reagents and
standards and standards are needed for sample preparation and analysis:
7.3.1 Water. Same as in Section 7.1.
7.3.2. Perchloric Acid (HClO4). Concentrated (70
percent V/V).
7.3.3 Nitric Acid (HNO3). Concentrated.
7.3.4 Beryllium Powder. Minimum purity 98 percent.
7.3.5 Sulfuric Acid (H2SO4) Solution, 12 N.
Dilute 33 ml of concentrated H2SO4 to 1 liter
with water.
7.3.6 Hydrochloric Acid Solution, 25 Percent HCl (V/V).
7.3.7 Stock Beryllium Standard Solution, 10 g Be/ml.
Dissolve 10.0 mg of Be in 80 ml of 12 N H2SO4 in
a 1000-ml volumetric flask. Dilute to volume with water. This solution
is stable for at least one month. Equivalent strength Be stock
solutions may be prepared from Be salts such as BeCl2 and
Be(NO3)2 (98 percent minimum purity).
7.3.8 Working Beryllium Standard Solution, 1 g Be/ml.
Dilute a 10 ml aliquot of the stock beryllium standard solution to 100
ml with 25 percent HCl solution to give a concentration of 1 mg/ml.
Prepare this dilute stock solution fresh daily.

8.0 Sample Collection, Preservation, Transport, and Storage

The amount of Be that is collected is generally small, therefore,
it is necessary to exercise particular care to prevent contamination or
loss of sample.
8.1 Pretest Preparation. Same as Method 5, Section 8.1, except
omit Section 8.1.3.
8.2 Preliminary Determinations. Same as Method 5, Section 8.2,
with the exception of the following:
8.2.1 Select a nozzle size based on the range of velocity heads to
assure that it is not necessary to change the nozzle size in order to
maintain isokinetic sampling rates below 28 liters/min (1.0 cfm).
8.2.2 Obtain samples over a period or periods of time that
accurately determine the maximum emissions that occur in a 24-hour
period. In the case of cyclic operations, perform sufficient sample
runs for the accurate determination of the emissions that occur over
the duration of the cycle. A minimum sample time of 2 hours per run is
recommended.
8.3 Preparation of Sampling Train. Same as Method 5, Section 8.3,
with the exception of the following:
8.3.1 Prior to assembly, clean all glassware (probe, impingers,
and connectors) by first soaking in wash acid for 2 hours, followed by
rinsing with water.
8.3.2 Save a portion of the water for a blank analysis.
8.3.3 Procedures relating to the use of metal probe liners are not
applicable.
8.3.4 Probe and filter heating systems are needed only if water
condensation is a problem. If this is the case, adjust the heaters to
provide a temperature at or above the stack temperature. However,
membrane filters such as the Millipore AA are limited to about 107
deg.C (225 deg.F). If the stack gas is in excess of about 93 deg.C
(200 deg.F), consideration should be given to an alternate procedure
such as moving the filter holder downstream of the first impinger to
insure that the filter does not exceed its temperature limit. After the
sampling train has been assembled, turn on and set the probe heating
system, if applicable, at the desired operating temperature. Allow time
for the temperatures to stabilize. Place crushed ice around the
impingers.

Note: An empty impinger may be inserted between the third
impinger and the silica gel to remove excess moisture from the
sample stream.

8.4 Leak Check Procedures, Sampling Train Operation, and
Calculation of Percent Isokinetic. Same as Method 5, Sections 8.4, 8.5,
and 8.6, respectively.
8.5 Sample Recovery. Same as Method 5, Section 8.7, except treat
the sample as follows: Transfer the probe and impinger assembly to a
cleanup area that is clean, protected from the wind, and free of Be
contamination. Inspect the train before and during this assembly, and
note any abnormal conditions. Treat the sample as follows: Disconnect
the probe from the impinger train.
8.5.1 Container No. 1. Same as Method 5, Section 8.7.6.1.
8.5.2 Container No. 2. Place the contents (measured to 1 ml) of
the first three impingers into a glass sample bottle. Use the
procedures outlined in Section 8.7.6.2 of Method 5, where applicable,
to rinse the probe nozzle, probe fitting, probe liner, filter holder,
and all glassware between the filter holder and the back half of the
third impinger with water. Repeat this procedure with acetone. Place
both water and acetone rinse solutions in the sample bottle with the
contents of the impingers.
8.5.3 Container No. 3. Same as Method 5, Section 8.7.6.3.
8.6 Blanks.
8.6.1 Water Blank. Save a portion of the water as a blank. Take
200 ml directly from the wash bottle being used and place it in a
plastic sample container labeled ``H2O blank.''
8.6.2 Filter. Save two filters from each lot of filters used in
sampling. Place these filters in a container labeled ``filter blank.''
8.7 Post-test Glassware Rinsing. If an additional test is desired,
the glassware can be carefully double rinsed with water and
reassembled. However, if the glassware is out of use more than 2 days,
repeat the initial acid wash procedure.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.4, 10.1..................... Sampling Ensure accuracy and
equipment leak precision of
checks and sampling
calibration. measurements.
10.2.......................... Spectrophotometer Ensure linearity of
calibration. spectrophotometer
response to
standards.
11.5.......................... Check for matrix Eliminate matrix
effects. effects.
11.6.......................... Audit sample Evaluate analyst's
analysis. technique and
standards
preparation.
------------------------------------------------------------------------

[[Page 62183]]

9.2 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 Sampling Equipment. Same as Method 5, Section 10.0.
10.2 Preparation of Standard Solutions. Pipet 1, 3, 5, 8, and 10
ml of the 1.0 g Be/ml working standard solution into separate
100 ml volumetric flasks, and dilute to the mark with water. The total
amounts of Be in these standards are 1, 3, 5, 8, and 10 g,
respectively.
10.3 Spectrophotometer and Recorder. The Be response may be
measured by either peak height or peak area. Analyze an aliquot of the
10-g standard at 234.8 nm using a nitrous oxide/acetylene
flame. Determine the maximum absorbance of the standard, and set this
value to read 90 percent of the recorder full scale.
10.4 Calibration Curve.
10.4.1 After setting the recorder scale, analyze an appropriately
sized aliquot of each standard and the BLANK (see Section 11) until two
consecutive peaks agree within 3 percent of their average value.
10.4.3 Subtract the average peak height (or peak area) of the
blank--which must be less than 2 percent of recorder full scale--from
the averaged peak heights of the standards. If the blank absorbance is
greater than 2 percent of full-scale, the probable cause is Be
contamination of a reagent or carry-over of Be from a previous sample.
Prepare the calibration curve by plotting the corrected peak height of
each standard solution versus the corresponding total Be weight in the
standard (in g).
10.5 Spectrophotometer Calibration Quality Control. Calculate the
least squares slope of the calibration curve. The line must pass
through the origin or through a point no further from the origin than
2 percent of the recorder full scale. Multiply the
corrected peak height by the reciprocal of the least squares slope to
determine the distance each calibration point lies from the theoretical
calibration line. The difference between the calculated concentration
values and the actual concentrations (i.e., 1, 3, 5, 8, and 10
g Be) must be less than 7 percent for all standards.

11.0 Analytical Procedure

11.1 Sample Loss Check. Prior to analysis, check the liquid level
in Container No. 2. Note on the analytical data sheet whether leakage
occurred during transport. If a noticeable amount of leakage occurred,
either void the sample or take steps, subject to the approval of the
Administrator, to adjust the final results.
11.2 Glassware Cleaning. Before use, clean all glassware according
to the procedure of Section 8.3.1.
11.3 Sample Preparation. The digestion of Be samples is
accomplished in part in concentrated HClO4.

Note: The sample must be heated to light brown fumes after the
initial HNO3 addition; otherwise, dangerous perchlorates may result
from the subsequent HClO4 digestion. HClO4
should be used only under a hood.

11.3.1 Container No. 1. Transfer the filter and any loose
particulate matter from Container No. 1 to a 150-ml beaker. Add 35 ml
concentrated HNO3. To oxidize all organic matter, heat on a
hotplate until light brown fumes are evident. Cool to room temperature,
and add 5 ml 12 N H2SO4 and 5 ml concentrated
HClO4.
11.3.2 Container No. 2. Place a portion of the water and acetone
sample into a 150 ml beaker, and put on a hotplate. Add portions of the
remainder as evaporation proceeds and evaporate to dryness. Cool the
residue, and add 35 ml concentrated HNO3. To oxidize all
organic matter, heat on a hotplate until light brown fumes are evident.
Cool to room temperature, and add 5 ml 12 N H2SO4
and 5 ml concentrated HClO4. Then proceed with step 11.3.4.
11.3.3 Final Sample Preparation. Add the sample from Section
11.3.2 to the 150-ml beaker from Section 11.3.1. Replace on a hotplate,
and evaporate to dryness in a HClO4 hood. Cool the residue
to room temperature, add 10.0 ml of 25 percent V/V HCl, and mix to
dissolve the residue.
11.3.4 Filter and Water Blanks. Cut each filter into strips, and
treat each filter individually as directed in Section 11.3.1. Treat the
200-ml water blank as directed in Section 11.3.2. Combine and treat
these blanks as directed in Section 11.3.3.
11.4 Spectrophotometer Preparation. Turn on the power; set the
wavelength, slit width, and lamp current; and adjust the background
corrector as instructed by the manufacturer's manual for the particular
atomic absorption spectrophotometer. Adjust the burner and flame
characteristics as necessary.
11.5 Analysis. Calibrate the analytical equipment and develop a
calibration curve as outlined in Sections 10.4 and 10.5.
11.5.1 Beryllium Samples. Repeat the procedure used to establish
the calibration curve with an appropriately sized aliquot of each
sample (from Section 11.3.3) until two consecutive peak heights agree
within 3 percent of their average value. The peak height of each sample
must be greater than 10 percent of the recorder full scale. If the peak
height of the sample is off scale on the recorder, further dilute the
original source sample to bring the Be concentration into the
calibration range of the spectrophotometer.
11.5.2 Run a blank and standard at least after every five samples
to check the spectrophotometer calibration. The peak height of the
blank must pass through a point no further from the origin than
2 percent of the recorder full scale. The difference
between the measured concentration of the standard (the product of the
corrected peak height and the reciprocal of the least squares slope)
and the actual concentration of the standard must be less than 7
percent, or recalibration of the analyzer is required.
11.5.3 Check for Matrix Effects (optional). Use the Method of
Standard Additions (see Reference 2 in Section 16.0) to check at least
one sample from each source for matrix effects on the Be results. If
the results of the Method of Standard Additions procedure used on the
single source sample do not agree to within 5 percent of the value
obtained by the routine atomic absorption analysis, then reanalyze all
samples from the source using the Method of Standard Additions
procedure.
11.6 Container No. 2 (Silica Gel). Weigh the spent silica gel (or
silica gel plus impinger) to the nearest 0.5 g using a balance. (This
step may be conducted in the field.)

12.0 Data Analysis and Calculations

K1 = 0.3858 deg.K/mm Hg for metric units.
= 17.64 deg.R/in. Hg for English units.
K3 = 10-\6\ g/g for metric units.
= 2.2046 x 10-\9\ lb/g for English units.
mBe = Total weight of beryllium in the source sample.
Ps = Absolute stack gas pressure, mm Hg (in. Hg).
t = Daily operating time, sec/day.
Ts = Absolute average stack gas temperature, deg.K
( deg.R).
Vm(std) = Dry gas sample volume at standard conditions, scm
(scf).
Vw(std) = Volume of water vapor at standard conditions, scm
(scf).

12.2 Average Dry Gas Meter Temperature and Average Orifice

[[Page 62184]]

Pressure Drop, Dry Gas Volume, Volume of Water Vapor Condensed,
Moisture Content, Isokinetic Variation, and Stack Gas Velocity and
Volumetric Flow Rate. Same as Method 5, Sections 12.2 through 12.5,
12.11, and 12.12, respectively.
12.3 Total Beryllium. For each source sample, correct the average
maximum absorbance of the two consecutive samples whose peak heights
agree within 3 percent of their average for the contribution of the
solution blank (see Sections 11.3.4 and 11.5.2). Correcting for any
dilutions if necessary, use the calibration curve and these corrected
averages to determine the total weight of Be in each source sample.
12.4 Beryllium Emission Rate. Calculate the daily Hg emission
rate, R, using Equation 104-1. For continuous operations, the operating
time is equal to 86,400 seconds per day. For cyclic operations, use
only the time per day each stack is in operation. The total Hg emission
rate from a source will be the summation of results from all stacks.
[GRAPHIC] [TIFF OMITTED] TR17OC00.505

12.5 Determination of Compliance. Each performance test consists
of three sample runs. For the purpose of determining compliance with an
applicable national emission standard, use the average of the results
of all sample runs.

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

Same as References 1, 2, and 4-11 of Section 16.0 of Method 101
with the addition of the following:

1. Amos, M.D., and J.B. Willis. Use of High-Temperature Pre-
Mixed Flames in Atomic Absorption Spectroscopy. Spectrochim. Acta.
22:1325. 1966.
2. Fleet, B., K.V. Liberty, and T. S. West. A Study of Some
Matrix Effects in the Determination of Beryllium by Atomic
Absorption Spectroscopy in the Nitrous Oxide-Acetylene Flame.
Talanta 17:203. 1970.

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

Method 105--Determination of Mercury in Wastewater Treatment Plant
Sewage Sludges

Note: This method does not include all of the specifications
(e.g., equipment and supplies) and procedures (e.g., sampling and
analytical) essential to its performance. Some material is
incorporated by reference from other methods in this part.
Therefore, to obtain reliable results, persons using this method
should also have a thorough knowledge of at least the following
additional test methods: Method 101 and Method 101A.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Mercury (Hg)................... 7439-97-6 Dependent upon
spectrophotometer and
recorder.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of total organic and inorganic Hg content in sewage sludges.
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 Time-composite sludge samples are withdrawn from the conveyor
belt subsequent to dewatering and before incineration or drying. A
weighed portion of the sludge is digested in aqua regia and is oxidized
by potassium permanganate (KMnO4). Mercury in the digested
sample is then measured by the conventional spectrophotometric cold-
vapor technique.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection and Mixing. The following items are required
for collection and mixing of the sludge samples:
6.1.1 Container. Plastic, 50-liter.
6.1.2 Scoop. To remove 950-ml (1 quart.) sludge sample.
6.1.3 Mixer. Mortar mixer, wheelbarrow-type, 57-liter (or
equivalent) with electricity-driven motor.
6.1.4 Blender. Waring-type, 2-liter.
6.1.5 Scoop. To remove 100-ml and 20-ml samples of blended sludge.
6.1.6 Erlenmeyer Flasks. Four, 125-ml.

[[Page 62185]]

6.1.7 Beakers. Glass beakers in the following sizes: 50 ml (1),
200 ml (1), 400 ml (2).
6.2 Sample Preparation and Analysis. Same as Method 101, Section
6.3, with the addition of the following:
6.2.1 Hot Plate.
6.2.2 Desiccator.
6.2.3 Filter Paper. S and S No. 588 (or equivalent).
6.2.4 Beakers. Glass beakers, 200 ml and 400 ml (2 each).

7.0 Reagents and Standards

7.1 Sample Analysis. Same as Method 101A, Section 7.2, with the
following additions and exceptions:
7.1.1 Hydrochloric Acid. The concentrated HCl specified in Method
101A, Section 7.2.4, is not required.
7.1.2 Aqua Regia. Prepare immediately before use. Carefully add
one volume of concentrated HNO3 to three volumes of
concentrated HCl.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Sludge Sampling. Withdraw equal volume increments of sludge
[for a total of at least 15 liters (16 quarts)] at intervals of 30 min
over an 8-hr period, and combine in a rigid plastic container.
8.2 Sludge Mixing. Transfer the entire 15-liter sample to a mortar
mixer. Mix the sample for a minimum of 30 min at 30 rpm. Take six 100-
ml portions of sludge, and combine in a 2-liter blender. Blend sludge
for 5 min; add water as necessary to give a fluid consistency.
Immediately after stopping the blender, withdraw four 20-ml portions of
blended sludge, and place them in separate, tared 125-ml Erlenmeyer
flasks. Reweigh each flask to determine the exact amount of sludge
added.
8.3 Sample Holding Time. Samples shall be analyzed within the time
specified in the applicable subpart of the regulations.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.0.......................... Spectrophotometer Ensure linearity of
calibration. spectrophotometer
response to
standards.
11.0.......................... Check for matrix Eliminate matrix
effects. effects.
------------------------------------------------------------------------

10.0 Calibration and Standardization

Same as Method 101A, Section 10.2.

11.0 Analytical Procedures

11.1 Solids Content of Blended Sludge. Dry one of the 20-ml
blended samples from Section 8.2 in an oven at 105 deg.C (221 deg.F)
to constant weight. Cool in a desiccator, weigh and record the dry
weight of the sample.
11.2 Aqua Regia Digestion of Blended Samples.
11.2.1 To each of the three remaining 20-ml samples from Section
8.2 add 25 ml of aqua regia, and digest the on a hot plate at low heat
(do not boil) for 30 min, or until samples are a pale yellow-brown
color and are void of the dark brown color characteristic of organic
matter. Remove from hotplate and allow to cool.
11.2.2 Filter each digested sample separately through an S and S
No. 588 filter or equivalent, and rinse the filter contents with 50 ml
of water. Transfer the filtrate and filter washing to a 100-ml
volumetric flask, and carefully dilute to volume with water.
11.3 Solids Content of the Sludge Before Blending. Remove two 100-
ml portions of mixed sludge from the mortar mixer and place in
separate, tared 400-ml beakers. Reweigh each beaker to determine the
exact amount of sludge added. Dry in oven at 105 deg.C (221 deg.F)
and cool in a desiccator to constant weight.
11.4 Analysis for Mercury. Analyze the three aqua regia-digested
samples using the procedures outlined in Method 101A, Section 11.0.

12.0 Data Analysis and Calculations

12.1 Nomenclature.

Cm = Concentration of Hg in the digested sample, g/
g.
Fsb = Weight fraction of solids in the blended sludge.
Fsm = Weight fraction of solids in the collected sludge
after mixing.
M = Hg content of the sewage sludge (on a dry basis), g/g.
m = Mass of Hg in the aliquot of digested sample analyzed, g.
n = number of digested samples (specified in Section 11.2 as three).
Va = Volume of digested sample analyzed, ml.
Vs = Volume of digested sample, ml.
Wb = Weight of empty sample beaker, g.
Wbs = Weight of sample beaker and sample, g.
Wbd = Weight of sample beaker and sample after drying, g.
Wf = Weight of empty sample flask, g.
Wfd = Weight of sample flask and sample after drying, g.
Wfs = Weight of sample flask and sample, g.

12.2 Mercury Content of Digested Sample (Wet Basis).
12.2.1 For each sample analyzed for Hg content, calculate the
arithmetic mean maximum absorbance of the two consecutive samples whose
peak heights agree 3 percent of their average. Correct this
average value for the contribution of the blank. Use the calibration
curve and these corrected averages to determine the final Hg
concentration in the solution cell for each sludge sample.
12.2.2 Calculate the average Hg concentration of the digested
samples by correcting for any dilutions made to bring the sample into
the working range of the spectrophotometer and for the weight of the
sludge portion digested, using Equation 105-1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.506

12.3 Solids Content of Blended Sludge. Determine the solids
content of the blended sludge using Equation 105-2.

[[Page 62186]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.507

12.4 Solids Content of Bulk Sample (before blending but, after
mixing in mortar mixer). Determine the solids content of each 100 ml
aliquot (Section 11.3), and average the results.
[GRAPHIC] [TIFF OMITTED] TR17OC00.508

12.5 Mercury Content of Bulk Sample (Dry Basis). Average the
results from the three samples from each 8-hr composite sample, and
calculate the Hg concentration of the composite sample on a dry basis.
[GRAPHIC] [TIFF OMITTED] TR17OC00.509

13.0 Method Performance

13.1 Range. The range of this method is 0.2 to 5 micrograms per
gram; it may be extended by increasing or decreasing sample size.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. Bishop, J.N. Mercury in Sediments. Ontario Water Resources
Commission. Toronto, Ontario, Canada. 1971.
2. Salma, M. Private Communication. EPA California/Nevada Basin
Office. Alameda, California.
3. Hatch, W.R. and W.L. Ott. Determination of Sub-Microgram
Quantities of Mercury by Atomic Absorption Spectrophotometry.
Analytical Chemistry. 40:2085. 1968.
4. Bradenberger, H., and H. Bader. The Determination of Nanogram
Levels of Mercury in Solution by a Flameless Atomic Absorption
Technique. Atomic Absorption Newsletter. 6:101. 1967.
5. Analytical Quality Control Laboratory (AQCL). Mercury in
Sediment (Cold Vapor Technique) (Provisional Method). U.S.
Environmental Protection Agency. Cincinnati, Ohio. April 1972.
6. Kopp, J.F., M.C. Longbottom, and L.B. Lobring. ``Cold Vapor''
Method for Determining Mercury. Journal AWWA. 64(1):20-25. 1972.
7. Manual of Methods for Chemical Analysis of Water and Wastes.
U.S. Environmental Protection Agency. Cincinnati, Ohio. Publication
No. EPA-624/2-74-003. December 1974. pp. 118-138.
8. Mitchell, W.J., M.R. Midgett, J. Suggs, R.J. Velton, and D.
Albrink. Sampling and Homogenizing Sewage for Analysis.
Environmental Monitoring and Support Laboratory, Office of Research
and Development, U.S. Environmental Protection Agency. Research
Triangle Park, N.C. March 1979. p. 7.

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

Method 106--Determination of Vinyl Chloride Emissions From
Stationary Sources

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Vinyl Chloride (CH2:CHCl)...... 75-01-4 Dependent upon
analytical equipment.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of vinyl chloride emissions from ethylene dichloride, vinyl chloride,
and polyvinyl chloride manufacturing processes. This method does not
measure vinyl chloride contained in particulate matter.
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 bag sample of stack gas containing vinyl
chloride is subjected to GC analysis using a flame ionization detector
(FID).

3.0 Definitions. [Reserved]

4.0 Interferences

4.1 Resolution interferences of vinyl chloride may be encountered
on some sources. Therefore, the chromatograph operator should select
the column and operating parameters best suited to the particular
analysis requirements. The selection made is subject to approval of the
Administrator. Approval is automatic, provided that confirming data are
produced through an adequate supplemental analytical technique, and
that the data are available for review by the Administrator. An example
of this would be analysis with a different column or GC/mass
spectroscopy.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection (see Figure 106-1). The sampling train
consists of the following components:
6.1.1 Probe. Stainless steel, borosilicate glass, Teflon tubing
(as stack temperature permits), or equivalent, equipped with a glass
wool plug to remove particulate matter.

[[Page 62187]]

6.1.2 Sample Lines. Teflon, 6.4-mm outside diameter, of sufficient
length to connect probe to bag. Use a new unused piece for each series
of bag samples that constitutes an emission test, and discard upon
completion of the test.
6.1.3 Quick Connects. Stainless steel, male (2) and female (2),
with ball checks (one pair without), located as shown in Figure 106-1.
6.1.4 Tedlar Bags. 50- to 100-liter capacity, to contain sample.
Aluminized Mylar bags may be used if the samples are analyzed within 24
hours of collection.
6.1.5 Bag Containers. Rigid leak-proof containers for sample bags,
with covering to protect contents from sunlight.
6.1.6 Needle Valve. To adjust sample flow rates.
6.1.7 Pump. Leak-free, with minimum of 2-liter/min capacity.
6.1.8 Charcoal Tube. To prevent admission of vinyl chloride and
other organics to the atmosphere in the vicinity of samplers.
6.1.9 Flowmeter. For observing sampling flow rate; capable of
measuring a flow range from 0.10 to 1.00 liter/min.
6.1.10 Connecting Tubing. Teflon, 6.4-mm outside diameter, to
assemble sampling train (Figure 106-1).
6.1.11 Tubing Fittings and Connectors. Teflon or stainless steel,
to assemble sampling training.
6.2 Sample Recovery. Teflon tubing, 6.4-mm outside diameter, to
connect bag to GC sample loop. Use a new unused piece for each series
of bag samples that constitutes an emission test, and discard upon
conclusion of analysis of those bags.
6.3 Analysis. The following equipment is required:
6.3.1 Gas Chromatograph. With FID potentiometric strip chart
recorder and 1.0 to 5.0-ml heated sampling loop in automatic sample
valve. The chromatographic system shall be capable of producing a
response to 0.1-ppmv vinyl chloride that is at least as great as the
average noise level. (Response is measured from the average value of
the base line to the maximum of the wave form, while standard operating
conditions are in use.)
6.3.2 Chromatographic Columns. Columns as listed below. Other
columns may be used provided that the precision and accuracy of the
analysis of vinyl chloride standards are not impaired and that
information is available for review confirming that there is adequate
resolution of vinyl chloride peak. (Adequate resolution is defined as
an area overlap of not more than 10 percent of the vinyl chloride peak
by an interferent peak. Calculation of area overlap is explained in
Procedure 1 of appendix C to this part: ``Determination of Adequate
Chromatographic Peak Resolution.'')
6.3.2.1 Column A. Stainless steel, 2.0 m by 3.2 mm, containing 80/
100-mesh Chromasorb 102.
6.3.2.2 Column B. Stainless steel, 2.0 m by 3.2 mm, containing 20
percent GE SF-96 on 60/ip-mesh Chromasorb P AW; or stainless steel, 1.0
m by 3.2 mm containing 80/100-mesh Porapak T. Column B is required as a
secondary column if acetaldehyde is present. If used, column B is
placed after column A. The combined columns should be operated at 120
deg.C (250 deg.F).
6.3.3 Rate Meters (2). Rotameter , or equivalent, 100-ml/min
capacity, with flow control valves.
6.3.4 Gas Regulators. For required gas cylinders.
6.3.5 Temperature Sensor. Accurate to 1 deg.C
(2 deg.F), to measure temperature of heated sample loop at
time of sample injection.
6.3.6 Barometer. Accurate to 5 mm Hg, to measure
atmospheric pressure around GC during sample analysis.
6.3.7 Pump. Leak-free, with minimum of 100-ml/min capacity.
6.3.8 Recorder. Strip chart type, optionally equipped with either
disc or electronic integrator.
6.3.9 Planimeter. Optional, in place of disc or electronic
integrator on recorder, to measure chromatograph peak areas.
6.4 Calibration and Standardization.
6.4.1 Tubing. Teflon, 6.4-mm outside diameter, separate pieces
marked for each calibration concentration.

Note: The following items are required only if the optional
standard gas preparation procedures (Section 10.1) are followed.

6.4.2 Tedlar Bags. Sixteen-inch-square size, with valve; separate
bag marked for each calibration concentration.
6.4.3 Syringes. 0.5-ml and 50-l, gas tight, individually
calibrated to dispense gaseous vinyl chloride.
6.4.4 Dry Gas Meter with Temperature and Pressure Gauges. Singer
Model DTM-115 with 802 index, or equivalent, to meter nitrogen in
preparation of standard gas mixtures, calibrated at the flow rate used
to prepare standards.

7.0 Reagents and Standards

7.1 Analysis. The following reagents are required for analysis.
7.1.1 Helium or Nitrogen. Purity 99.9995 percent or greater, for
chromatographic carrier gas.
7.1.2 Hydrogen. Purity 99.9995 percent or greater.
7.1.3 Oxygen or Air. Either oxygen (purity 99.99 percent or
greater) or air (less than 0.1 ppmv total hydrocarbon content), as
required by detector.
7.2 Calibration. Use one of the following options: either Sections
7.2.1 and 7.2.2, or Section 7.2.3.
7.2.1 Vinyl Chloride. Pure vinyl chloride gas certified by the
manufacturer to contain a minimum of 99.9 percent vinyl chloride. If
the gas manufacturer maintains a bulk cylinder supply of 99.9+ percent
vinyl chloride, the certification analysis may have been performed on
this supply, rather than on each gas cylinder prepared from this bulk
supply. The date of gas cylinder preparation and the certified analysis
must have been affixed to the cylinder before shipment from the gas
manufacturer to the buyer.
7.2.2 Nitrogen. Same as described in Section 7.1.1.
7.2.3 Cylinder Standards. Gas mixture standards (50-,10-, and 5
ppmv vinyl chloride) in nitrogen cylinders may be used to directly
prepare a chromatograph calibration curve as described in Section 10.3
if the following conditions are met: (a) The manufacturer certifies the
gas composition with an accuracy of 3 percent or better.
(b) The manufacturer recommends a maximum shelf life over which the gas
concentration does not change by greater than 5 percent
from the certified value. (c) The manufacturer affixes the date of gas
cylinder preparation, certified vinyl chloride concentration, and
recommended maximum shelf to the cylinder before shipment to the buyer.
7.2.3.1 Cylinder Standards Certification. The manufacturer shall
certify the concentration of vinyl chloride in nitrogen in each
cylinder by (a) directly analyzing each cylinder and (b) calibrating
his analytical procedure on the day of cylinder analysis. To calibrate
his analytical procedure, the manufacturer shall use as a minimum, a
three point calibration curve. It is recommended that the manufacturer
maintain (1) a high concentration calibration standard (between 50 and
100 ppmv) to prepare his calibration curve by an appropriate dilution
technique and (2) a low-concentration calibration standard (between 5
and 10 ppmv) to verify the dilution technique used. If the difference
between the apparent concentration read from the calibration curve and
the true concentration assigned to the low-concentration calibration
standard exceeds 5 percent of the true concentration, the manufacturer
shall

[[Page 62188]]

determine the source of error and correct it, then repeat the three-
point calibration.
7.2.3.2 Verification of Manufacturer's Calibration Standards.
Before using a standard, the manufacturer shall verify each calibration
standard (a) by comparing it to gas mixtures prepared (with 99 mole
percent vinyl chloride) in accordance with the procedure described in
Section 7.2.1 or (b) calibrating it against vinyl chloride cylinder
Standard Reference Materials (SRM's) prepared by the National Institute
of Standards and Technology, if such SRM's are available. The agreement
between the initially determined concentration value and the
verification concentration value must be 5 percent. The
manufacturer must reverify all calibration standards on a time interval
consistent with the shelf life of the cylinder standards sold.
7.2.4 Audit Cylinder Standards.
7.2.4.1 Gas mixture standards with concentrations known only to
the person supervising the analysis of samples. The concentrations of
the audit cylinders should be: one low-concentration cylinder in the
range of 5 to 20 ppmv vinyl chloride and one high-concentration
cylinder in the range of 20 to 50 ppmv. When available, obtain audit
samples from the appropriate EPA Regional Office or from the
responsible enforcement authority.

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

7.2.4.2 Alternatively, audit cylinders obtained from a commercial
gas manufacturer may be used provided: (a) the gas meets the conditions
described in Section 7.2.3, (b) the gas manufacturer certifies the
audit cylinder as described in Section 7.2.3.1, and (c) the gas
manufacturer obtains an independent analysis of the audit cylinders to
verify this analysis. Independent analysis is defined here to mean
analysis performed by an individual different than the individual who
performs the gas manufacturer's analysis, while using calibration
standards and analysis equipment different from those used for the gas
manufacturer's analysis. Verification is complete and acceptable when
the independent analysis concentration is within 5 percent of the gas
manufacturer's concentration.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Bag Leak-Check. The following leak-check procedure is
recommended, but not required, prior to sample collection. The post-
test leak-check procedure is mandatory. Connect a water manometer and
pressurize the bag to 5 to 10 cm H2O (2 to 4 in.
H2O). Allow to stand for 10 min. Any displacement in the
water manometer indicates a leak. Also, check the rigid container for
leaks in this manner.

Note: An alternative leak-check method is to pressurize the bag
to 5 to 10 cm H2O and allow it to stand overnight. A deflated bag
indicates a leak. For each sample bag in its rigid container, place
a rotameter in line between the bag and the pump inlet. Evacuate the
bag. Failure of the rotameter to register zero flow when the bag
appears to be empty indicates a leak.

8.2 Sample Collection. Assemble the sample train as shown in
Figure 106-1. Join the quick connects as illustrated, and determine
that all connection between the bag and the probe are tight. Place the
end of the probe at the centroid of the stack and start the pump with
the needle valve adjusted to yield a flow that will fill over 50
percent of bag volume in the specific sample period. After allowing
sufficient time to purge the line several times, change the vacuum line
from the container to the bag and evacuate the bag until the rotameter
indicates no flow. Then reposition the sample and vacuum lines and
begin the actual sampling, keeping the rate proportional to the stack
velocity. At all times, direct the gas exiting the rotameter away from
sampling personnel. At the end of the sample period, shut off the pump,
disconnect the sample line from the bag, and disconnect the vacuum line
from the bag container. Protect the bag container from sunlight.
8.3 Sample Storage. Keep the sample bags out of direct sunlight.
When at all possible, analysis is to be performed within 24 hours, but
in no case in excess of 72 hours of sample collection. Aluminized Mylar
bag samples must be analyzed within 24 hours.
8.4 Post-test Bag Leak-Check. Subsequent to recovery and analysis
of the sample, leak-check the sample bag according to the procedure
outlined in Section 8.1.

9.0 Quality Control

9.1 Miscellaneous Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.3.......................... Chromatograph Ensure precision and
calibration. accuracy of
chromatograph.
11.1.......................... Audit sample Evaluate analytical
analysis. technique and
standards
preparation.
------------------------------------------------------------------------

9.2 Immediately after the preparation of the calibration curve and
prior to the sample analyses, perform the analysis audit described in
Appendix C, Procedure 2: ``Procedure for Field Auditing GC Analysis.''

10.0 Calibration and Standardization

Note: Maintain a laboratory log of all calibrations.

10.1 Preparation of Vinyl Chloride Standard Gas Mixtures.
(Optional Procedure-delete if cylinder standards are used.) Evacuate a
16-inch square Tedlar bag that has passed a leak-check (described in
Section 8.1) and meter in 5.0 liters of nitrogen. While the bag is
filling, use the 0.5-ml syringe to inject 250 l of 99.9+
percent vinyl chloride gas through the wall of the bag. Upon
withdrawing the syringe, immediately cover the resulting hole with a
piece of adhesive tape. The bag now contains a vinyl chloride
concentration of 50 ppmv. In a like manner use the 50 l
syringe to prepare gas mixtures having 10-and 5-ppmv vinyl chloride
concentrations. Place each bag on a smooth surface and alternately
depress opposite sides of the bag 50 times to further mix the gases.
These gas mixture standards may be used for 10 days from the date of
preparation, after which time new gas mixtures must be prepared.
(Caution: Contamination may be a problem when a bag is reused if the
new gas mixture standard is a lower concentration than the previous gas
mixture standard.)
10.2 Determination of Vinyl Chloride Retention Time. (This section
can be performed simultaneously with Section 10.3.) Establish
chromatograph conditions identical with those in Section 11.3.
Determine proper attenuator position. Flush the sampling loop with
helium or nitrogen and activate the sample valve. Record the injection
time, sample loop temperature, column temperature, carrier gas flow

[[Page 62189]]

rate, chart speed, and attenuator setting. Record peaks and detector
responses that occur in the absence of vinyl chloride. Maintain
conditions with the equipment plumbing arranged identically to Section
11.2, and flush the sample loop for 30 seconds at the rate of 100 ml/
min with one of the vinyl chloride calibration mixtures. Then activate
the sample valve. Record the injection time. Select the peak that
corresponds to vinyl chloride. Measure the distance on the chart from
the injection time to the time at which the peak maximum occurs. This
quantity divided by the chart speed is defined as the retention time.
Since other organics may be present in the sample, positive
identification of the vinyl chloride peak must be made.
10.3 Preparation of Chromatograph Calibration Curve. Make a GC
measurement of each gas mixture standard (described in Section 7.2.3 or
10.1) using conditions identical to those listed in Sections 11.2 and
11.3. Flush the sampling loop for 30 seconds at the rate of 100 ml/min
with one of the standard mixtures, and activate the sample valve.
Record the concentration of vinyl chloride injected (Cc),
attenuator setting, chart speed, peak area, sample loop temperature,
column temperature, carrier gas flow rate, and retention time. Record
the barometric pressure. Calculate Ac, the peak area
multiplied by the attenuator setting. Repeat until two consecutive
injection areas are within 5 percent, then plot the average of those
two values versus Cc. When the other standard gas mixtures
have been similarly analyzed and plotted, draw a straight line through
the points derived by the least squares method. Perform calibration
daily, or before and after the analysis of each emission test set of
bag samples, whichever is more frequent. For each group of sample
analyses, use the average of the two calibration curves which bracket
that group to determine the respective sample concentrations. If the
two calibration curves differ by more than 5 percent from their mean
value, then report the final results by both calibration curves.

11.0 Analytical Procedure

11.1 Audit Sample Analysis. Immediately after the preparation of
the calibration curve and prior to the sample analyses, perform the
analysis audit described in Procedure 2 of appendix C to this part:
``Procedure for Field Auditing GC Analysis.''
11.2 Sample Recovery. With a new piece of Teflon tubing identified
for that bag, connect a bag inlet valve to the gas chromatograph sample
valve. Switch the valve to receive gas from the bag through the sample
loop. Arrange the equipment so the sample gas passes from the sample
valve to 100-ml/min rotameter with flow control valve followed by a
charcoal tube and a 1-in. H2O pressure gauge. Maintain the
sample flow either by a vacuum pump or container pressurization if the
collection bag remains in the rigid container. After sample loop
purging is ceased, allow the pressure gauge to return to zero before
activating the gas sampling valve.
11.3 Analysis.
11.3.1 Set the column temperature to 100 deg.C (210 deg.F) and
the detector temperature to 150 deg.C (300 deg.F). When optimum
hydrogen and oxygen (or air) flow rates have been determined, verify
and maintain these flow rates during all chromatography operations.
Using helium or nitrogen as the carrier gas, establish a flow rate in
the range consistent with the manufacturer's requirements for
satisfactory detector operation. A flow rate of approximately 40 ml/min
should produce adequate separations. Observe the base line periodically
and determine that the noise level has stabilized and that base line
drift has ceased. Purge the sample loop for 30 seconds at the rate of
100 ml/min, shut off flow, allow the sample loop pressure to reach
atmospheric pressure as indicated by the H2O manometer, then
activate the sample valve. Record the injection time (the position of
the pen on the chart at the time of sample injection), sample number,
sample loop temperature, column temperature, carrier gas flow rate,
chart speed, and attenuator setting. Record the barometric pressure.
From the chart, note the peak having the retention time corresponding
to vinyl chloride as determined in Section 10.2. Measure the vinyl
chloride peak area, Am, by use of a disc integrator,
electronic integrator, or a planimeter. Measure and record the peak
heights, Hm. Record Am and retention time. Repeat
the injection at least two times or until two consecutive values for
the total area of the vinyl chloride peak agree within 5 percent of
their average. Use the average value for these two total areas to
compute the bag concentration.
11.3.2 Compare the ratio of Hm to Am for the
vinyl chloride sample with the same ratio for the standard peak that is
closest in height. If these ratios differ by more than 10 percent, the
vinyl chloride peak may not be pure (possibly acetaldehyde is present)
and the secondary column should be employed (see Section 6.3.2.2).
11.4 Determination of Bag Water Vapor Content. Measure the ambient
temperature and barometric pressure near the bag. From a water
saturation vapor pressure table, determine and record the water vapor
content of the bag, Bwb, as a decimal figure. (Assume the
relative humidity to be 100 percent unless a lesser value is known.)

12.0 Calculations and Data Analysis

12.1 Nomenclature.

Am = Measured peak area.
Af = Attenuation factor.
Bwb = Water vapor content of the bag sample, as analyzed,
volume fraction.
Cb = Concentration of vinyl chloride in the bag, ppmv.
Cc = Concentration of vinyl chloride in the standard sample,
ppmv.
Pi = Laboratory pressure at time of analysis, mm Hg.
Pr = Reference pressure, the laboratory pressure recorded
during calibration, mm Hg.
Ti = Absolute sample loop temperature at the time of
analysis, deg.K ( deg.R).
Tr = Reference temperature, the sample loop temperature
recorded during calibration, deg.K ( deg.R).

12.2 Sample Peak Area. Determine the sample peak area,
Ac, as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.510

12.3 Vinyl Chloride Concentration. From the calibration curves
prepared in Section 10.3, determine the average concentration value of
vinyl chloride, Cc, that corresponds to Ac, the
sample peak area. Calculate the concentration of vinyl chloride in the
bag, Cb, as follows:

[[Page 62190]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.511

13.0 Method Performance

13.1 Analytical Range. This method is designed for the 0.1 to 50
parts per million by volume (ppmv) range. However, common gas
chromatograph (GC) instruments are capable of detecting 0.02 ppmv vinyl
chloride. With proper calibration, the upper limit may be extended as
needed.

14.0 Pollution Prevention, [Reserved]

15.0 Waste Management, [Reserved]

16.0 References

1. Brown D.W., E.W. Loy, and M.H. Stephenson. Vinyl Chloride
Monitoring Near the B. F. Goodrich Chemical Company in Louisville,
KY. Region IV, U.S. Environmental Protection Agency, Surveillance
and Analysis Division, Athens, GA. June 24, 1974.
2. G.D. Clayton and Associates. Evaluation of a Collection and
Analytical Procedure for Vinyl Chloride in Air. U.S. Environmental
Protection Agency, Research Triangle Park, N.C. EPA Contract No. 68-
02-1408, Task Order No. 2, EPA Report No. 75-VCL-1. December 13,
1974.
3. Midwest Research Institute. Standardization of Stationary
Source Emission Method for Vinyl Chloride. U.S. Environmental
Protection Agency, Research Triangle Park, N.C. Publication No. EPA-
600/4-77-026. May 1977.
4. Scheil, G. and M.C. Sharp. Collaborative Testing of EPA
Method 106 (Vinyl Chloride) that Will Provide for a Standardized
Stationary Source Emission Measurement Method. U.S. Environmental
Protection Agency, Research Triangle Park, N.C. Publication No. EPA
600/4-78-058. October 1978.

17.0 Tables, Diagrams Flowcharts, and Validation Data.

BILLING CODE 6560-50-P

[[Page 62191]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.512

BILLING CODE 6560-50-C

[[Page 62192]]

Method 107--Determination of Vinyl Chloride Content of In-Process
Wastewater Samples, and Vinyl Chloride Content of Polyvinyl
Chloride Resin Slurry, Wet Cake, and Latex Samples

Note: Performance of this method should not be attempted by
persons unfamiliar with the operation of a gas chromatograph (GC)
nor by those who are unfamiliar with source sampling, because
knowledge beyond the scope of this presentation is required. 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
106.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Vinyl Chloride (CH2:CHCl)...... 75-01-4 Dependent upon
analytical equipment.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of the vinyl chloride monomer (VCM) content of in-process wastewater
samples, and the residual vinyl chloride monomer (RCVM) content of
polyvinyl chloride (PVC) resins, wet, cake, slurry, and latex samples.
It cannot be used for polymer in fused forms, such as sheet or cubes.
This method is not acceptable where methods from section 304(h) of the
Clean Water Act, 33 U.S.C. 1251 et seq. (the Federal Water Pollution
Control Amendments of 1972 as amended by the Clean Water Act of 1977)
are required.
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 The basis for this method relates to the vapor equilibrium
that is established at a constant known temperature in a closed system
between RVCM, PVC resin, water, and air. The RVCM in a PVC resin will
equilibrate rapidly in a closed vessel, provided that the temperature
of the PVC resin is maintained above the glass transition temperature
of that specific resin.
2.2 A sample of PVC or in-process wastewater is collected in a
vial or bottle and is conditioned. The headspace in the vial or bottle
is then analyzed for vinyl chloride using gas chromatography with a
flame ionization detector.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 The chromatograph columns and the corresponding operating
parameters herein described normally provide an adequate resolution of
vinyl chloride; however, resolution interferences may be encountered on
some sources. Therefore, the chromatograph operator shall select the
column and operating parameters best suited to his particular analysis
requirements, subject to the approval of the Administrator. Approval is
automatic provided that confirming data are produced through an
adequate supplemental analytical technique, such as analysis with a
different column or GC/mass spectroscopy, and that these data are made
available for review by the Administrator.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. The following equipment is required:
6.1.1 Glass bottles. 60-ml (2-oz) capacity, with wax-lined screw-
on tops, for PVC samples.
6.1.2 Glass Vials. Headspace vials, with Teflon-faced butyl rubber
sealing discs, for water samples.
6.1.3 Adhesive Tape. To prevent loosening of bottle tops.
6.2 Sample Recovery. The following equipment is required:
6.2.1 Glass Vials. Headspace vials, with butyl rubber septa and
aluminum caps. Silicone rubber is not acceptable.
6.2.2 Analytical Balance. Capable of determining sample weight
within an accuracy of 1 percent.
6.2.3 Vial Sealer. To seal headspace vials.
6.2.4 Syringe. 100-ml capacity.
6.3 Analysis. The following equipment is required:
6.3.1 Headspace Sampler and Chromatograph. Capable of sampling and
analyzing a constant amount of headspace gas from a sealed vial, while
maintaining that vial at a temperature of 90 deg.C 0.5
deg.C (194 deg.F 0.9 deg.F). The chromatograph shall be
equipped with a flame ionization detector (FID). Perkin-Elmer
Corporation Models F-40, F-42, F-45, HS-6, and HS-100, and Hewlett-
Packard Corporation Model 19395A have been found satisfactory.
Chromatograph backflush capability may be required.
6.3.2 Chromatographic Columns. Stainless steel 1 m by 3.2 mm and 2
m by 3.2 mm, both containing 50/80-mesh Porapak Q. Other columns may be
used provided that the precision and accuracy of the analysis of vinyl
chloride standards are not impaired and information confirming that
there is adequate resolution of the vinyl chloride peak are available
for review. (Adequate resolution is defined as an area overlap of not
more than 10 percent of the vinyl chloride peak by an interferant peak.
Calculation of area overlap is explained in Procedure 1 of appendix C
to this part: ``Determination of Adequate Chromatographic Peak
Resolution.'') Two 1.83 m columns, each containing 1 percent Carbowax
1500 on Carbopak B, have been found satisfactory for samples containing
acetaldehyde.
6.3.3 Temperature Sensor. Range 0 to 100 deg.C (32 to 212 deg.F)
accurate to 0.1 deg.C.
6.3.4 Integrator-Recorder. To record chromatograms.
6.3.5 Barometer. Accurate to 1 mm Hg.

[[Continued on page 62193]]

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

[[pp. 62143-62192]] Amendments for Testing and Monitoring Provisions

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