[[pp. 62193-62242]] 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 62193-62242]
From the Federal Register Online via GPO Access [wais.access.gpo.gov]
[DOCID:fr17oc00-19]

[[Continued from page 62192]]

[[Page 62193]]

6.3.6 Regulators. For required gas cylinders.
6.3.7 Headspace Vial Pre-Pressurizer. Nitrogen pressurized
hypodermic needle inside protective shield.

7.0 Reagents and Standards

7.1 Analysis. Same as Method 106, Section 7.1, with the addition
of the following:
7.1.1 Water. Interference-free.
7.2 Calibration. The following items are required for calibration:
7.2.1 Cylinder Standards (4). Gas mixture standards (50-, 500-,
2000- and 4000-ppm vinyl chloride in nitrogen cylinders). Cylinder
standards may be used directly to 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 (see Section 7.2.1.1). (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 life to the cylinder before shipment to the
buyer.
7.2.1.1 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
the analytical procedure on the day of cylinder analysis. To calibrate
the analytical procedure, the manufacturer shall use, as a minimum, a
3-point calibration curve. It is recommended that the manufacturer
maintain (1) a high-concentration calibration standard (between 4000
and 8000 ppm) to prepare the calibration curve by an appropriate
dilution technique and (2) a low-concentration calibration standard
(between 50 and 500 ppm) 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 determine the source of error and correct it, then
repeat the 3-point calibration.
7.2.1.2 Verification of Manufacturer's Calibration Standards.
Before using, the manufacturer shall verify each calibration standard
by (a) comparing it to gas mixtures prepared (with 99 mole percent
vinyl chloride) in accordance with the procedure described in Section
10.1 of Method 106 or by (b) calibrating it against vinyl chloride
cylinder Standard Reference Materials (SRMs) prepared by the National
Institute of Standards and Technology, if such SRMs are available. The
agreement between the initially determined concentration value and the
verification concentration value must be within 5 percent. The
manufacturer must reverify all calibration standards on a time interval
consistent with the shelf life of the cylinder standards sold.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Sample Collection.
8.1.1 PVC Sampling. Allow the resin or slurry to flow from a tap
on the tank or silo until the tap line has been well purged. Extend and
fill a 60-ml sample bottle under the tap, and immediately tighten a cap
on the bottle. Wrap adhesive tape around the cap and bottle to prevent
the cap from loosening. Place an identifying label on each bottle, and
record the date, time, and sample location both on the bottles and in a
log book.
8.1.2 Water Sampling. At the sampling location fill the vials
bubble-free to overflowing so that a convex meniscus forms at the top.
The excess water is displaced as the sealing disc is carefully placed,
with the Teflon side down, on the opening of the vial. Place the
aluminum seal over the disc and the neck of the vial, and crimp into
place. Affix an identifying label on the bottle, and record the date,
time, and sample location both on the vials and in a log book.
8.2 Sample Storage. All samples must be analyzed within 24 hours
of collection, and must be refrigerated during this period.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.3.......................... Chromatograph Ensure precision and
calibration. accuracy of
chromatograph.
------------------------------------------------------------------------

10.0 Calibration and Standardization

Note: Maintain a laboratory log of all calibrations.

10.1 Preparation of Standards. Calibration standards are prepared
as follows: Place 100 l or about two equal drops of distilled
water in the sample vial, then fill the vial with the VCM/nitrogen
standard, rapidly seat the septum, and seal with the aluminum cap. Use
a \1/8\-in. stainless steel line from the cylinder to the vial. Do not
use rubber or Tygon tubing. The sample line from the cylinder must be
purged (into a properly vented hood) for several minutes prior to
filling the vials. After purging, reduce the flow rate to between 500
and 1000 cc/min. Place end of tubing into vial (near bottom). Position
a septum on top of the vial, pressing it against the \1/8\-in. filling
tube to minimize the size of the vent opening. This is necessary to
minimize mixing air with the standard in the vial. Each vial is to be
purged with standard for 90 seconds, during which time the filling tube
is gradually slid to the top of the vial. After the 90 seconds, the
tube is removed with the septum, simultaneously sealing the vial.
Practice will be necessary to develop good technique. Rubber gloves
should be worn during the above operations. The sealed vial must then
be pressurized for 60 seconds using the vial prepressurizer. Test the
vial for leakage by placing a drop of water on the septum at the needle
hole. Prepressurization of standards is not required unless samples
have been prepressurized.
10.2 Analyzer Calibration. Calibration is to be performed each 8-
hour period the chromatograph is used. Alternatively, calibration with
duplicate 50-, 500-, 2,000-, and 4,000-ppm standards (hereafter
described as a four-point calibration) may be performed on a monthly
basis, provided that a calibration confirmation test consisting of
duplicate analyses of an appropriate standard is performed once per
plant shift, or once per chromatograph carrousel operation (if the
chromatograph operation is less frequent than once per shift). The
criterion for acceptance of each calibration confirmation test is that
both analyses of 500-ppm standards [2,000-ppm standards if dispersion
resin (excluding latex resin) samples are being analyzed] must be
within 5 percent of the most recent four-point calibration curve. If
this criterion is not met, then a complete four-point calibration must
be performed before sample analyses can proceed.

[[Page 62194]]

10.3 Preparation of Chromatograph Calibration Curve. Prepare two
vials each of 50-, 500-, 2,000-, and 4,000-ppm standards. Run the
calibration samples in exactly the same manner as regular samples. Plot
As, the integrator area counts for each standard sample,
versus Cc, the concentration of vinyl chloride in each
standard sample. Draw a straight line through the points derived by the
least squares method.

11.0 Analytical Procedure

11.1 Preparation of Equipment. Install the chromatographic column
and condition overnight at 160 deg.C (320 deg.F). In the first
operation, Porapak columns must be purged for 1 hour at 230 deg.C (450
deg.F).
Do not connect the exit end of the column to the detector while
conditioning. Hydrogen and air to the detector must be turned off while
the column is disconnected.
11.2 Flow Rate Adjustments. Adjust flow rates as follows:
11.2.1. Nitrogen Carrier Gas. Set regulator on cylinder to read 50
psig. Set regulator on chromatograph to produce a flow rate of 30.0 cc/
min. Accurately measure the flow rate at the exit end of the column
using the soap film flowmeter and a stopwatch, with the oven and column
at the analysis temperature. After the instrument program advances to
the ``B'' (backflush) mode, adjust the nitrogen pressure regulator to
exactly balance the nitrogen flow rate at the detector as was obtained
in the ``A'' mode.
11.2.2. Vial Prepressurizer Nitrogen.
11.2.2.1 After the nitrogen carrier is set, solve the following
equation and adjust the pressure on the vial prepressurizer
accordingly.
[GRAPHIC] [TIFF OMITTED] TR17OC00.599

Where:

T1 = Ambient temperature, deg.K ( deg.R).
T2 = Conditioning bath temperature, deg.K ( deg.R).
P1 = Gas chromatograph absolute dosing pressure (analysis
mode), k Pa.
Pw1 = Water vapor pressure 525.8 mm Hg @ 90 deg.C.
Pw2 = Water vapor pressure 19.8 mm Hg @ 22 deg.C.
7.50 = mm Hg per k Pa.
10 kPa = Factor to adjust the prepressurized pressure to slightly less
than the dosing pressure.

11.2.2.2 Because of gauge errors, the apparatus may over-
pressurize the vial. If the vial pressure is at or higher than the
dosing pressure, an audible double injection will occur. If the vial
pressure is too low, errors will occur on resin samples because of
inadequate time for head-space gas equilibrium. This condition can be
avoided by running several standard gas samples at various pressures
around the calculated pressure, and then selecting the highest pressure
that does not produce a double injection. All samples and standards
must be pressurized for 60 seconds using the vial prepressurizer. The
vial is then placed into the 90 deg.C conditioning bath and tested for
leakage by placing a drop of water on the septum at the needle hole. A
clean, burr-free needle is mandatory.
11.2.3. Burner Air Supply. Set regulator on cylinder to read 50
psig. Set regulator on chromatograph to supply air to burner at a rate
between 250 and 300 cc/min. Check with bubble flowmeter.
11.2.4. Hydrogen Supply. Set regulator on cylinder to read 30
psig. Set regulator on chromatograph to supply approximately 35
5 cc/min. Optimize hydrogen flow to yield the most
sensitive detector response without extinguishing the flame. Check flow
with bubble meter and record this flow.
11.3 Temperature Adjustments. Set temperatures as follows:
11.3.1. Oven (chromatograph column), 140 deg.C (280 deg.F).
11.3.2. Dosing Line, 150 deg.C (300 deg.F).
11.3.3. Injection Block, 170 deg.C (340 deg.F).
11.3.4. Sample Chamber, Water Temperature, 90 deg.C
1.0 deg.C (194 deg.F 1.8 deg.F).
11.4 Ignition of Flame Ionization Detector. Ignite the detector
according to the manufacturer's instructions.
11.5 Amplifier Balance. Balance the amplifier according to the
manufacturer's instructions.
11.6 Programming the Chromatograph. Program the chromatograph as
follows:
11.6.1. I -- Dosing or Injection Time. The normal setting is 2
seconds.
11.6.2. A -- Analysis Time. The normal setting is approximately 70
percent of the VCM retention time. When this timer terminates, the
programmer initiates backflushing of the first column.
11.6.3. B -- Backflushing Time. The normal setting is double the
analysis time.
11.6.4. W -- Stabilization Time. The normal setting is 0.5 min to
1.0 min.
11.6.5. X -- Number of Analyses Per Sample. The normal setting is
one.
11.7. Sample Treatment. All samples must be recovered and analyzed
within 24 hours after collection.
11.7.1 Resin Samples. The weight of the resin used must be between
0.1 and 4.5 grams. An exact weight must be obtained (within
1 percent) for each sample. In the case of suspension
resins, a volumetric cup can be prepared for holding the required
amount of sample. When the cup is used, open the sample bottle, and add
the cup volume of resin to the tared sample vial (tared, including
septum and aluminum cap). Obtain the exact sample weight, add 100 ml or
about two equal drops of water, and immediately seal the vial. Report
this value on the data sheet; it is required for calculation of RVCM.
In the case of dispersion resins, the cup cannot be used. Weigh the
sample in an aluminum dish, transfer the sample to the tared vial, and
accurately weigh it in the vial. After prepressurization of the
samples, condition them for a minimum of 1 hour in the 90 deg.C (190
deg.F) bath. Do not exceed 5 hours. Prepressurization is not required
if the sample weight, as analyzed, does not exceed 0.2 gram. It is also
not required if solution of the prepressurization equation yields an
absolute prepressurization value that is within 30 percent of the
atmospheric pressure.

Note: Some aluminum vial caps have a center section that must be
removed prior to placing into sample tray. If the cap is not
removed, the injection needle will be damaged.

11.7.2 Suspension Resin Slurry and Wet Cake Samples. Decant the
water from a wet cake sample, and turn the sample bottle upside down
onto a paper towel. Wait for the water to drain, place approximately
0.2 to 4.0 grams of the wet cake sample in a tared vial (tared,
including septum and aluminum cap) and seal immediately. Then determine
the sample weight (1 percent). All samples weighing over 0.2 gram, must
be prepressurized prior to conditioning for 1 hour at 90 deg.C (190
deg.F), except as noted in Section 11.7.1. A sample of wet cake is used
to determine total solids (TS). This is required for calculating the
RVCM.
11.7.3 Dispersion Resin Slurry and Geon Latex Samples. The
materials

[[Page 62195]]

should not be filtered. Sample must be thoroughly mixed. Using a tared
vial (tared, including septum and aluminum cap) add approximately eight
drops (0.25 to 0.35 g) of slurry or latex using a medicine dropper.
This should be done immediately after mixing. Seal the vial as soon as
possible. Determine sample weight (1 percent). Condition the vial for 1
hour at 90 deg.C (190 deg.F) in the analyzer bath. Determine the TS
on the slurry sample (Section 11.10).
11.7.4 In-process Wastewater Samples. Using a tared vial (tared,
including septum and aluminum cap) quickly add approximately 1 cc of
water using a medicine dropper. Seal the vial as soon as possible.
Determine sample weight (1 percent). Condition the vial for 1 hour at
90 deg.C (190 deg.F) in the analyzer bath.
11.8 Preparation of Sample Turntable.
11.8.1 Before placing any sample into turntable, be certain that
the center section of the aluminum cap has been removed. The numbered
sample vials should be placed in the corresponding numbered positions
in the turntable. Insert samples in the following order:
11.8.1.1 Positions 1 and 2. Old 2000-ppm standards for
conditioning. These are necessary only after the analyzer has not been
used for 24 hours or longer.
11.8.1.2 Position 3. 50-ppm standard, freshly prepared.
11.8.1.3 Position 4. 500-ppm standard, freshly prepared.
11.8.1.4 Position 5. 2000-ppm standard, freshly prepared.
11.8.1.5 Position 6. 4000-ppm standard, freshly prepared.
11.8.1.6 Position 7. Sample No. 7 (This is the first sample of the
day, but is given as 7 to be consistent with the turntable and the
integrator printout.)
11.8.2 After all samples have been positioned, insert the second
set of
50-, 500-, 2000-, and 4000-ppm standards. Samples, including standards,
must be conditioned in the bath of 90 deg.C (190 deg.F) for a minimum
of one hour and a maximum of five hours.
11.9 Start Chromatograph Program. When all samples, including
standards, have been conditioned at 90 deg.C (190 deg.F) for at least
one hour, start the analysis program according to the manufacturer's
instructions. These instructions must be carefully followed when
starting and stopping a program to prevent damage to the dosing
assembly.
11.10 Determination of Total Solids. For wet cake, slurry, resin
solution, and PVC latex samples, determine TS for each sample by
accurately weighing approximately 3 to 4 grams of sample in an aluminum
pan before and after placing in a draft oven (105 to 110 deg.C (221 to
230 deg.F)). Samples must be dried to constant weight. After first
weighing, return the pan to the oven for a short period of time, and
then reweigh to verify complete dryness. The TS are then calculated as
the final sample weight divided by initial sample weight.

12.0 Calculations and Data Analysis

12.1 Nomenclature.

As = Chromatogram area counts of vinyl chloride for the
sample, area counts.
As = Chromatogram area counts of vinyl chloride for the
sample.
Cc = Concentration of vinyl chloride in the standard sample,
ppm.
Kp = Henry's Law Constant for VCM in PVC 90 deg.C, 6.52 x
10-\6\ g/g/mm Hg.
Kw = Henry's Law Constant for VCM in water 90 deg.C, 7 x
10-\7\ g/g/mm Hg.
Mv = Molecular weight of VCM, 62.5 g/mole.
m = Sample weight, g.
Pa = Ambient atmospheric pressure, mm Hg.
R = Gas constant, (62360 \3\ ml) (mm Hg)/(mole)( deg.K).
Rf = Response factor in area counts per ppm VCM.
Rs = Response factor, area counts/ppm.
Tl = Ambient laboratory temperature, deg.K.
TS = Total solids expressed as a decimal fraction.
T2 = Equilibrium temperature, deg.K.
Vg = Volume of vapor phase, ml.
[GRAPHIC] [TIFF OMITTED] TR17OC00.513

Vv = Vial volume,\3\ ml.
1.36 = Density of PVC at 90 deg.C, g/\3\ ml.
0.9653 = Density of water at 90 deg.C,
g/\3\ ml.

12.2 Response Factor. If the calibration curve described in
Section 10.3 passes through zero, an average response factor,
Rf, may be used to facilitate computation of vinyl chloride
sample concentrations.
12.2.1 To compute Rf, first compute a response factor,
Rs, for each sample as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.514

12.2.2 Sum the individual response factors, and calculate
Rf. If the calibration curve does not pass through zero, use
the calibration curve to determine each sample concentration.
12.3 Residual Vinyl Chloride Monomer Concentration,
(Crvc) or Vinyl Chloride Monomer Concentration. Calculate
Crvc in ppm or mg/kg as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.515

Note: Results calculated using these equations represent
concentration based on the total sample. To obtain results based on
dry PVC content, divide by TS.

13.0 Method Performance

13.1 Range and Sensitivity. The lower limit of detection of vinyl
chloride will vary according to the sampling and chromatographic
system. The system should be capable of producing a measurement for a
50-ppm vinyl chloride standard that is at least

[[Page 62196]]

10 times the standard deviation of the system background noise level.
13.2 An interlaboratory comparison between seven laboratories of
three resin samples, each split into three parts, yielded a standard
deviation of 2.63 percent for a sample with a mean of 2.09 ppm, 4.16
percent for a sample with a mean of 1.66 ppm, and 5.29 percent for a
sample with a mean of 62.66 ppm.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. B.F. Goodrich, Residual Vinyl Chloride Monomer Content of
Polyvinyl Chloride Resins, Latex, Wet Cake, Slurry and Water
Samples. B.F. Goodrich Chemical Group Standard Test Procedure No.
1005-E. B.F. Goodrich Technical Center, Avon Lake, Ohio. October 8,
1979.
2. Berens, A.R. The Diffusion of Vinyl Chloride in Polyvinyl
Chloride. ACS-Division of Polymer Chemistry, Polymer Preprints 15
(2):197. 1974.
3. Berens, A.R. The Diffusion of Vinyl Chloride in Polyvinyl
Chloride. ACS-Division of Polymer Chemistry, Polymer Preprints 15
(2):203. 1974.
4. Berens, A.R., et. al. Analysis for Vinyl Chloride in PVC
Powders by Head-Space Gas Chromatography. Journal of Applied Polymer
Science. 19:3169-3172. 1975.
5. Mansfield, R.A. The Evaluation of Henry's Law Constant (Kp)
and Water Enhancement in the Perkin-Elmer Multifract F-40 Gas
Chromatograph. B.F. Goodrich. Avon Lake, Ohio. February 10, 1978.

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

Method 108--Determination of Particulate and Gaseous Arsenic
Emissions

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 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 12.

1.0 Scope and Application.

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Arsenic compounds as arsenic 7440-38-2 Lower limit 10 g/ml or less.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of inorganic As emissions from stationary 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

Particulate and gaseous As emissions are withdrawn isokinetically
from the source and are collected on a glass mat filter and in water.
The collected arsenic is then analyzed by means of atomic absorption
spectrophotometry (AAS).

3.0 Definitions. [Reserved]

4.0 Interferences

Analysis for As by flame AAS is sensitive to the chemical
composition and to the physical properties (e.g., viscosity, pH) of the
sample. The analytical procedure includes a check for matrix effects
(Section 11.5).

5.0 Safety

5.1 This method may involve hazardous materials, operations, and
equipment. This test method may not address all of the safety problems
associated with its use. It is the responsibility of the user to
establish appropriate safety and health practices and determine the
applicability of regulatory limitations prior to performing this test
method.
5.2 Corrosive reagents. The following reagents are hazardous.
Personal protective equipment and safe procedures that prevent chemical
splashes are recommended. 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 corrosive liquid with toxic
vapors. Vapors are highly irritating to eyes, skin, nose, and lungs,
causing severe damage. May cause bronchitis, pneumonia, or edema of
lungs. Exposure to concentrations of 0.13 to 0.2 percent can be lethal
to humans in a few minutes. Provide ventilation to limit exposure.
Reacts with metals, producing hydrogen gas.
5.2.2 Hydrogen Peroxide (H2O2). Very harmful
to eyes. 30% H2O2 can burn skin, nose, and lungs.
5.2.3 Nitric Acid (HNO3). Highly corrosive to eyes,
skin, nose, and lungs. Vapors are highly toxic and can 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.
5.2.4 Sodium Hydroxide (NaOH). Causes severe damage to eyes and
skin. Inhalation causes irritation to nose, throat, and lungs. Reacts
exothermically with small amounts of water.

6.0 Equipment and Supplies

6.1 Sample Collection. A schematic of the sampling train used in
performing this method is shown in Figure 108-1; it is similar to the
Method 5 sampling train of 40 CFR Part 60, Appendix A. The following
items are required for sample collection:
6.1.1 Probe Nozzle, Probe Liner, Pitot Tube, Differential Pressure
Gauge, Filter Holder, Filter Heating System, Temperature Sensor,
Metering System, Barometer, and Gas Density Determination Equipment.
Same as Method 5, Sections 6.1.1.1 to 6.1.1.7, 6.1.1.9, 6.1.2, and
6.1.3, respectively.
6.1.2 Impingers. Four 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 the
Greenburg-Smith design, modified by replacing the tip with a 1.3-cm ID
(0.5-in.) glass tube extending to about 1.3 cm (0.5 in.) from the
bottom of the flask. For the second impinger, use the Greenburg-Smith
design with the standard tip. Modifications (e.g., flexible connections
between the impingers, materials other than glass, or flexible vacuum
lines to connect the filter holder to the condenser) are subject to the
approval of the Administrator.
6.1.3 Temperature Sensor. Place a temperature sensor, capable of
measuring temperature to within 1 deg.C (2 deg.F), at the outlet of
the fourth impinger for monitoring purposes.
6.2 Sample Recovery. The following items are required for sample
recovery:
6.2.1 Probe-Liner and Probe-Nozzle Brushes, Petri Dishes,
Graduated Cylinder and/or Balance, Plastic Storage Containers, and
Funnel and Rubber Policeman. Same as Method 5, Sections 6.2.1 and 6.2.4
to 6.2.8, respectively.
6.2.2 Wash Bottles. Polyethylene (2).
6.2.3 Sample Storage Containers. Chemically resistant,
polyethylene or

[[Page 62197]]

polypropylene for glassware washes, 500- or 1000-ml.
6.3 Analysis. The following items are required for analysis:
6.3.1 Spectrophotometer. Equipped with an electrodeless discharge
lamp and a background corrector to measure absorbance at 193.7
nanometers (nm). For measuring samples having less than 10 g
As/ml, use a vapor generator accessory or a graphite furnace.
6.3.2 Recorder. To match the output of the spectrophotometer.
6.3.3 Beakers. 150 ml.
6.3.4 Volumetric Flasks. Glass 50-, 100-, 200-, 500-, and 1000-ml;
and polypropylene, 50-ml.
6.3.5 Balance. To measure within 0.5 g.
6.3.6 Volumetric Pipets. 1-, 2-, 3-,
5-, 8-, and 10-ml.
6.3.7 Oven.
6.3.8 Hot Plate.

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 The following reagents are required for sample collection:
7.1.1 Filters. Same as Method 5, Section 7.1.1, except that the
filters need not be unreactive to SO2.
7.1.2 Silica Gel, Crushed Ice, and Stopcock Grease. Same as Method
5, Sections 7.1.2, 7.1.4, and 7.1.5, respectively.
7.1.3 Water. Deionized distilled to meet ASTM D 1193-77 or 91
(incorporated by reference-see Sec. 61.18), Type 3. When high
concentrations of organic matter are not expected to be present, the
KMnO4 test for oxidizable organic matter may be omitted.
7.2 Sample Recovery.
7.2.1 0.1 N NaOH. Dissolve 4.00 g of NaOH in about 500 ml of water
in a 1-liter volumetric flask. Then, dilute to exactly 1.0 liter with
water.
7.3 Analysis. The following reagents and standards are required
for analysis:
7.3.1 Water. Same as Section 7.1.3.
7.3.2 Sodium Hydroxide, 0.1 N. Same as in Section 7.2.1.
7.3.3 Sodium Borohydride (NaBH4), 5 Percent Weight by
Volume (W/V). Dissolve 50.0 g of NaBH4 in about 500 ml of
0.1 N NaOH in a 1-liter volumetric flask. Then, dilute to exactly 1.0
liter with 0.1 N NaOH.
7.3.4 Hydrochloric Acid, Concentrated.
7.3.5 Potassium Iodide (KI), 30 Percent (W/V). Dissolve 300 g of
KI in 500 ml of water in a 1 liter volumetric flask. Then, dilute to
exactly 1.0 liter with water.
7.3.6 Nitric Acid, Concentrated.
7.3.7 Nitric Acid, 0.8 N. Dilute 52 ml of concentrated
HNO3 to exactly 1.0 liter with water.
7.3.8 Nitric Acid, 50 Percent by Volume (V/V). Add 50 ml
concentrated HNO3 to 50 ml water.
7.3.9 Stock Arsenic Standard, 1 mg As/ml. Dissolve 1.3203 g of
primary standard grade As2O3 in 20 ml of 0.1 N
NaOH in a 150 ml beaker. Slowly add 30 ml of concentrated
HNO3. Heat the resulting solution and evaporate just to
dryness. Transfer the residue quantitatively to a 1-liter volumetric
flask, and dilute to 1.0 liter with water.
7.3.10 Arsenic Working Solution, 1.0 g As/ml. Pipet
exactly 1.0 ml of stock arsenic standard into an acid-cleaned,
appropriately labeled 1-liter volumetric flask containing about 500 ml
of water and 5 ml of concentrated HNO3. Dilute to exactly
1.0 liter with water.
7.3.11 Air. Suitable quality for AAS analysis.
7.3.12 Acetylene. Suitable quality for AAS analysis.
7.3.13 Nickel Nitrate, 5 Percent Ni (W/V). Dissolve 24.780 g of
nickel nitrate hexahydrate
[Ni(NO3)26H2O] in water in a 100-ml
volumetric flask, and dilute to 100 ml with water.
7.3.14 Nickel Nitrate, 1 Percent Ni (W/V). Pipet 20 ml of 5
percent nickel nitrate solution into a 100-ml volumetric flask, and
dilute to exactly 100 ml with water.
7.3.15 Hydrogen Peroxide, 3 Percent by Volume. Pipet 50 ml of 30
percent H2O2 into a 500-ml volumetric flask, and
dilute to exactly 500 ml with water.
7.3.16 Quality Assurance Audit Samples. When making compliance
determinations, and upon availability, audit samples may be obtained
from the appropriate EPA regional Office or from the responsible
enforcement authority.

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

8.0 Sample Collection, Preservation, Transport, and Storage

8.1 Pretest Preparation. Follow the general procedure given in
Method 5, Section 8.1, except the filter need not be weighed, and the
200 ml of 0.1N NaOH and Container 4 should be tared to within 0.5 g.
8.2 Preliminary Determinations. Follow the general procedure given
in Method 5, Section 8.2, except select the nozzle size to maintain
isokinetic sampling rates below 28 liters/min (1.0 cfm).
8.3 Preparation of Sampling Train. Follow the general procedure
given in Method 5, Section 8.3.
8.4 Leak-Check Procedures. Same as Method 5, Section 8.4.
8.5 Sampling Train Operation. Follow the general procedure given
in Method 5, Section 8.5, except maintain isokinetic sampling flow
rates below 28 liters/min (1.0 cfm). For each run, record the data
required on a data sheet similar to the one shown in Figure 108-2.
8.6 Calculation of Percent Isokinetic. Same as Method 5, Section
8.6.
8.7 Sample Recovery. Same as Method 5, Section 8.7, except that
0.1 N NaOH is used as the cleanup solvent instead of acetone and that
the impinger water is treated as follows:
8.7.1 Container Number 4 (Impinger Water). Clean each of the first
three impingers and connecting glassware in the following manner:
8.7.1.1 Wipe the impinger ball joints free of silicone grease, and
cap the joints.
8.7.1.2 Rotate and agitate each of the first two impingers, using
the impinger contents as a rinse solution.
8.7.1.3 Transfer the liquid from the first three impingers to
Container Number 4. Remove the outlet ball-joint cap, and drain the
contents through this opening. Do not separate the impinger parts
(inner and outer tubes) while transferring their contents to the
container.
8.7.1.4 Weigh the contents of Container No. 4 to within 0.5 g.
Record in the log the weight of liquid along with a notation of any
color or film observed in the impinger catch. The weight of liquid is
needed along with the silica gel data to calculate the stack gas
moisture content.

Note: Measure and record the total amount of 0.1 N NaOH used for
rinsing under Sections 8.7.1.5 and 8.7.1.6.

8.7.1.5 Pour approximately 30 ml of 0.1 NaOH into each of the
first two impingers, and agitate the impingers. Drain the 0.1 N NaOH
through the outlet arm of each impinger into Container Number 4. Repeat
this operation a second time; inspect the impingers for any abnormal
conditions.
8.7.1.6 Wipe the ball joints of the glassware connecting the
impingers and the back half of the filter holder free of silicone
grease, and rinse each piece of glassware twice with 0.1 N NaOH;
transfer this rinse into Container Number 4. (DO NOT RINSE or brush the
glass-fritted filter support.) Mark the height of the fluid level to
determine whether leakage occurs during transport. Label the container
to identify clearly its contents.

[[Page 62198]]

8.8 Blanks.
8.8.1 Sodium Hydroxide. Save a portion of the 0.1 N NaOH used for
cleanup as a blank. Take 200 ml of this solution directly from the wash
bottle being used and place it in a plastic sample container labeled
``NaOH blank.''
8.8.2 Water. Save a sample of the water, and place it in a
container labeled ``H2O blank.''
8.8.3 Filter. Save two filters from each lot of filters used in
sampling. Place these filters in a container labeled ``filter blank.''

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

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

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.
10.2.1 For the high level procedure, pipet 1, 3, 5, 8, and 10 ml
of the 1.0 mg As/ml stock solution into separate 100 ml volumetric
flasks, each containing 5 ml of concentrated HNO3. Dilute to
the mark with water.
10.2.2 For the low level vapor generator procedure, pipet 1, 2, 3,
and 5 ml of 1.0 g As/ml standard solution into separate
reaction tubes. Dilute to the mark with water.
10.2.3 For the low level graphite furnace procedure, pipet 1, 5,
10 and 15 ml of 1.0 g As/ml standard solution into separate
flasks along with 2 ml of the 5 percent nickel nitrate solution and 10
ml of the 3 percent H2O2 solution. Dilute to the
mark with water.
10.3 Calibration Curve. Analyze a 0.8 N HNO3 blank and
each standard solution according to the procedures outlined in section
11.4.1. Repeat this procedure on each standard solution until two
consecutive peaks agree within 3 percent of their average value.
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 height of each standard solution. If the blank absorbance is
greater than 2 percent of full-scale, the probable cause is As
contamination of a reagent or carry-over of As from a previous sample.
Prepare the calibration curve by plotting the corrected peak height of
each standard solution versus the corresponding final total As weight
in the solution.
10.4 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 (e.g., 1, 3, 5, 8, and 10 mg As
for the high-level procedure) must be less than 7 percent for all
standards.

Note: For instruments equipped with direct concentration readout
devices, preparation of a standard curve will not be necessary. In
all cases, follow calibration and operational procedures in the
manufacturers' instruction manual.

11.0 Analytical Procedure

11.1 Sample Loss Check. Prior to analysis, check the liquid level
in Containers Number 2 and Number 4. 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 Sample Preparation.
11.2.1 Container Number 1 (Filter). Place the filter and loose
particulate matter in a 150 ml beaker. Also, add the filtered solid
material from Container Number 2 (see Section 11.2.2). Add 50 ml of 0.1
N NaOH. Then stir and warm on a hot plate at low heat (do not boil) for
about 15 minutes. Add 10 ml of concentrated HNO3, bring to a
boil, then simmer for about 15 minutes. Filter the solution through a
glass fiber filter. Wash with hot water, and catch the filtrate in a
clean 150 ml beaker. Boil the filtrate, and evaporate to dryness. Cool,
add 5 ml of 50 percent HNO3, and then warm and stir. Allow
to cool. Transfer to a 50-ml volumetric flask, dilute to volume with
water, and mix well.
11.2.2 Container Number 2 (Probe Wash).
11.2.2.1 Filter (using a glass fiber filter) the contents of
Container Number 2 into a 200 ml volumetric flask. Combine the filtered
(solid) material with the contents of Container Number 1 (Filter).
11.2.2.2 Dilute the filtrate to exactly 200 ml with water. Then
pipet 50 ml into a 150 ml beaker. Add 10 ml of concentrated
HNO3, bring to a boil, and evaporate to dryness. Allow to
cool, add 5 ml of 50 percent HNO3, and then warm and stir.
Allow the solution to cool, transfer to a 50-ml volumetric flask,
dilute to volume with water, and mix well.
11.2.3 Container Number 4 (Impinger Solution). Transfer the
contents of Container Number 4 to a 500 ml volumetric flask, and dilute
to exactly 500-ml with water. Pipet 50 ml of the solution into a 150-ml
beaker. Add 10 ml of concentrated HNO3, bring to a boil, and
evaporate to dryness. Allow to cool, add 5 ml of 50 percent
HNO3, and then warm and stir. Allow the solution to cool,
transfer to a 50-ml volumetric flask, dilute to volume with water, and
mix well.
11.2.4 Filter Blank. Cut each filter into strips, and treat each
filter individually as directed in Section 11.2.1, beginning with the
sentence, ``Add 50 ml of 0.1 N NaOH.''
11.2.5 Sodium Hydroxide and Water Blanks. Treat separately 50 ml
of 0.1 N NaOH and 50 ml water, as directed under Section 11.2.3,
beginning with the sentence, ``Pipet 50 ml of the solution into a 150-
ml beaker.''
11.3 Spectrophotometer Preparation. Turn on the power; set the
wavelength, slit width, and lamp current. 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.
11.4 Analysis. Calibrate the analytical equipment and develop a
calibration curve as outlined in Sections 10.2 through 10.4.
11.4.1 Arsenic Samples. Analyze an appropriately sized aliquot of
each diluted sample (from Sections 11.2.1

[[Page 62199]]

through 11.2.3) until two consecutive peak heights agree within 3
percent of their average value. If applicable, follow the procedures
outlined in Section 11.4.1.1. If the sample concentration falls outside
the range of the calibration curve, make an appropriate dilution with
0.8 N HNO3 so that the final concentration falls within the
range of the curve. Using the calibration curve, determine the arsenic
concentration in each sample fraction.

Note: Because instruments vary between manufacturers, no
detailed operating instructions will be given here. Instead, the
instrument manufacturer's detailed operating instructions should be
followed.

11.4.1.1 Arsenic Determination at Low Concentration. The lower
limit of flame AAS is 10 g As/ml. If the arsenic concentration
of any sample is at a lower level, use the graphite furnace or vapor
generator which is available as an accessory component. Flame, graphite
furnace, or vapor generators may be used for samples whose
concentrations are between 10 and 30 g/ml. Follow the
manufacturer's instructions in the use of such equipment.
11.4.1.1.1 Vapor Generator Procedure. Place a sample containing
between 0 and 5 g of arsenic in the reaction tube, and dilute
to 15 ml with water. Since there is some trial and error involved in
this procedure, it may be necessary to screen the samples by
conventional atomic absorption until an approximate concentration is
determined. After determining the approximate concentration, adjust the
volume of the sample accordingly. Pipet 15 ml of concentrated HCl into
each tube. Add 1 ml of 30 percent KI solution. Place the reaction tube
into a 50 deg.C (120 deg.F) water bath for 5 minutes. Cool to room
temperature. Connect the reaction tube to the vapor generator assembly.
When the instrument response has returned to baseline, inject 5.0 ml of
5 percent NaBH4, and integrate the resulting
spectrophotometer signal over a 30-second time period.
11.4.1.1.2 Graphite Furnace Procedure. Dilute the digested sample
so that a 5 ml aliquot contains less than 1.5 g of arsenic.
Pipet 5 ml of this digested solution into a 10-ml volumetric flask. Add
1 ml of the 1 percent nickel nitrate solution, 0.5 ml of 50 percent
HNO3, and 1 ml of the 3 percent hydrogen peroxide and dilute
to 10 ml with water. The sample is now ready for analysis.
11.4.1.2 Run a blank (0.8 N HNO3) 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 average 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.
11.4.1.3 Determine the arsenic concentration in the filter blank
(i.e., the average of the two blank values from each lot).
11.4.2 Container Number 3 (Silica Gel). This step may be conducted
in the field. Weigh the spent silica gel (or silica gel plus impinger)
to the nearest 0.5 g; record this weight.
11.5 Check for matrix effects on the arsenic results. Same as
Method 12, Section 11.5.
11.6 Audit Sample Analysis.
11.6.1 When the method is used to analyze samples to demonstrate
compliance with a source emission regulation, a set of EPA audit
samples must be analyzed, subject to availability.
11.6.2 Concurrently analyze the audit samples and the compliance
samples in the same manner to evaluate the technique of the analyst and
the standards preparation.

Note: It is recommended that known quality control samples be
analyzed prior to the compliance and audit sample analyses to
optimize the system accuracy and precision. These quality control
samples may be obtained by contacting the appropriate EPA regional
Office or the responsible enforcement authority.

11.6.3 The same analyst, analytical reagents, and analytical
system shall be used for the compliance samples and the EPA audit
samples. If this condition is met, duplicate auditing of subsequent
compliance analyses for the same enforcement agency within a 30-day
period is waived. An audit sample set may not be used to validate
different sets of compliance samples under the jurisdiction of separate
enforcement agencies, unless prior arrangements have been made with
both enforcement agencies.
11.7 Audit Sample Results.
11.7.1 Calculate the audit sample concentrations in g/
m3 and submit results using the instructions provided with
the audit samples.
11.7.2 Report the results of the audit samples and the compliance
determination samples along with their identification numbers, and the
analyst's name to the responsible enforcement authority. Include this
information with reports of any subsequent compliance analyses for the
same enforcement authority during the 30-day period.
11.7.3 The concentrations of the audit samples obtained by the
analyst shall agree within 10 percent of the actual concentrations. If
the 10 percent specification is not met, reanalyze the compliance and
audit samples, and include initial and reanalysis values in the test
report.
11.7.4 Failure to meet the 10 percent specification may require
retests until the audit problems are resolved. However, if the audit
results do not affect the compliance or noncompliance status of the
affected facility, the Administrator may waive the reanalysis
requirement, further audits, or retests and accept the results of the
compliance test. While steps are being taken to resolve audit analysis
problems, the Administrator may also choose to use the data to
determine the compliance or noncompliance status of the affected
facility.

12.0 Data Analysis and Calculations

12.1 Nomenclature.

Bws = Water in the gas stream, proportion by volume.
Ca = Concentration of arsenic as read from the standard
curve, g/ml.
Cc = Actual audit concentration, g/m3.
Cd, = Determined audit concentration, g/m3.
Cs = Arsenic concentration in stack gas, dry basis,
converted to standard conditions, g/dsm3 (gr/dscf).
Ea = Arsenic mass emission rate, g/hr (lb/hr).
Fd = Dilution factor (equals 1 if the sample has not been
diluted).
I = Percent of isokinetic sampling.
mbi = Total mass of all four impingers and contents before
sampling, g.
mfi = Total mass of all four impingers and contents after
sampling, g.
mn = Total mass of arsenic collected in a specific part of
the sampling train, g.
mt = Total mass of arsenic collected in the sampling train,
g.
Tm = Absolute average dry gas meter temperature (see Figure
108-2), deg.K ( deg.R).
Vm = Volume of gas sample as measured by the dry gas meter,
dry basis, m3 (ft3).
Vm(std) = Volume of gas sample as measured by the dry gas
meter, corrected to standard conditions, m3
(ft3).
Vn = Volume of solution in which the arsenic is contained,
ml.
Vw(std) = Volume of water vapor collected in the sampling
train, corrected to standard conditions, m3
(ft3).
H = Average pressure differential across the orifice meter
(see Figure 108-2), mm H2O (in. H2O).

[[Page 62200]]

12.2 Average Dry Gas Meter Temperatures (Tm) and
Average Orifice Pressure Drop (H). See data sheet (Figure 108-
2).
12.3 Dry Gas Volume. Using data from this test, calculate
Vm(std) according to the procedures outlined in Method 5,
Section 12.3.
12.4 Volume of Water Vapor.
[GRAPHIC] [TIFF OMITTED] TR17OC00.516

Where:

K2 = 0.001334 m\3\/g for metric units.
= 0.047012 ft\3\/g for English units.

12.5 Moisture Content.
[GRAPHIC] [TIFF OMITTED] TR17OC00.517

12.6 Amount of Arsenic Collected.
12.6.1 Calculate the amount of arsenic collected in each part of
the sampling train, as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.518

12.6.2 Calculate the total amount of arsenic collected in the
sampling train as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.519

12.7 Calculate the arsenic concentration in the stack gas (dry
basis, adjusted to standard conditions) as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.520

Where:

K3 = 10-\6\ g/g for metric units
= 1.54 x 10-\5\ gr/g for English units

12.8 Stack Gas Velocity and Volumetric Flow Rate. Calculate the
average stack gas velocity and volumetric flow rate using data obtained
in this method and the equations in Sections 12.2 and 12.3 of Method 2.
12.9 Pollutant Mass Rate. Calculate the arsenic mass emission rate
as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.521

12.10 Isokinetic Variation. Same as Method 5, Section 12.11.

13.0 Method Performance

13.1 Sensitivity. The lower limit of flame AAS 10 g As/
ml. The analytical procedure includes provisions for the use of a
graphite furnace or vapor generator for samples with a lower arsenic
concentration.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References.

Same as References 1 through 9 of Method 5, Section 17.0, with the
addition of the following:

1. Perkin Elmer Corporation. Analytical Methods for Atomic
Absorption Spectrophotometry. 303-0152. Norwalk, Connecticut.
September 1976. pp. 5-6.
2. Standard Specification for Reagent Water. In: Annual Book of
American Society for Testing and Materials Standards. Part 31:
Water, Atmospheric Analysis. American Society for Testing and
Materials. Philadelphia, PA. 1974. pp. 40-42.
3. Stack Sampling Safety Manual (Draft). U.S. Environmental
Protection Agency, Office of Air Quality Planning and Standard,
Research Triangle Park, NC. September 1978.

[[Page 62201]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.522

[[Page 62202]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.523

BILLING CODE 6560-50-C

[[Page 62203]]

Method 108A--Determination of Arsenic Content in Ore Samples From
Nonferrous Smelters

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 Appendix A to 40 CFR
part 60. Therefore, to obtain reliable results, persons using this
method should have a thorough knowledge of Method 12.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Arsenic compounds as arsenic 7440-38-2........ Lower limit 10 g/ml or less.
------------------------------------------------------------------------

1.2 Applicability. This method applies to the determination of
inorganic As content of process ore and reverberatory matte samples
from nonferrous smelters 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

Arsenic bound in ore samples is liberated by acid digestion and
analyzed by flame atomic absorption spectrophotometry (AAS).

3.0 Definitions [Reserved]

4.0 Interferences

5.0 Safety

5.1 Disclaimer. This method may involve hazardous materials,
operations, and equipment. This test method may not address all of the
safety problems associated with its use. It is the responsibility of
the user 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 that prevent chemical
splashes are recommended. 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 corrosive liquid with toxic
vapors. Vapors are highly irritating to eyes, skin, nose, and lungs,
causing severe damage. May cause bronchitis, pneumonia, or edema of
lungs. Exposure to concentrations of 0.13 to 0.2 percent can be lethal
to humans in a few minutes. Provide ventilation to limit exposure.
Reacts with metals, producing hydrogen gas.
5.2.2 Hydrofluoric Acid (HF). Highly corrosive to eyes, skin,
nose, throat, and lungs. Reaction to exposure may be delayed by 24
hours or more. Provide ventilation to limit exposure.
5.2.3 Hydrogen Peroxide (H2O2). Very harmful
to eyes. 30% H2O2 can burn skin, nose, and lungs.
5.2.4 Nitric Acid (HNO3). Highly corrosive to eyes,
skin, nose, and lungs. Vapors are highly toxic and can 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.
5.2.5 Sodium Hydroxide (NaOH). Causes severe damage to eyes and
skin. Inhalation causes irritation to nose, throat, and lungs. Reacts
exothermically with limited amounts of water.

6.0 Equipment and Supplies

6.1 Sample Collection and Preparation. The following items are
required for sample collection and preparation:
6.1.1 Parr Acid Digestion Bomb. Stainless steel with vapor-tight
Teflon cup and cover.
6.1.2 Volumetric Pipets. 2- and 5-ml sizes.
6.1.3 Volumetric Flask. 50-ml polypropylene with screw caps, (one
needed per standard).
6.1.4 Funnel. Polyethylene or polypropylene.
6.1.5 Oven. Capable of maintaining a temperature of approximately
105 deg.C (221 deg.F).
6.1.6 Analytical Balance. To measure to within 0.1 mg.
6.2 Analysis. The following items are required for analysis:
6.2.1 Spectrophotometer and Recorder. Equipped with an
electrodeless discharge lamp and a background corrector to measure
absorbance at 193.7 nm. For measuring samples having less than 10
g As/ml, use a graphite furnace or vapor generator accessory.
The recorder shall match the output of the spectrophotometer.
6.2.2 Volumetric Flasks. Class A, 50-ml (one needed per sample and
blank), 500-ml, and 1-liter.
6.2.3 Volumetric Pipets. Class A,
1-, 5-, 10-, and 25-ml sizes.

7.0 Reagents and Standards.

[[Page 62204]]

7.1.9 Nickel Nitrate, 1 Percent Ni (W/V). Pipet 20 ml of 5 percent
nickel nitrate solution into a 100-ml volumetric flask, and dilute to
100 ml with water.
7.2 Analysis. The following reagents and standards are required
for analysis:
7.2.1 Water. Same as in Section 7.1.1.
7.2.2 Sodium Hydroxide, 0.1 N. Dissolve 2.00 g of NaOH in water in
a 500-ml volumetric flask. Dilute to volume with water.
7.2.3 Nitric Acid, 0.5 N. Same as in Section 7.1.3.
7.2.4 Potassium Chloride Solution, 10 percent. Same as in Section
7.1.5.
7.2.5 Hydrochloric Acid, Concentrated.
7.2.6 Potassium Iodide (KI), 30 Percent (W/V). Dissolve 300 g of
KI in about 500 ml of water in a 1-liter volumetric flask. Then, dilute
to exactly 1.0 liter with water.
7.2.7 Hydrogen Peroxide, 3 Percent by Volume. Pipet 50 ml of 30
percent H2O2 into a 500-ml volumetric flask, and
dilute to exactly 500 ml with water.
7.2.8 Stock Arsenic Standard, 1 mg As/ml. Dissolve 1.3203 g of
primary grade As2O3 in 20 ml of 0.1 N NaOH.
Slowly add 30 ml of concentrated HNO3, and heat in an oven
at 105 deg.C (221 deg.F) for 2 hours. Allow to cool, and dilute to 1
liter with deionized distilled water.
7.2.9 Nitrous Oxide. Suitable quality for AAS analysis.
7.2.10 Acetylene. Suitable quality for AAS analysis.
7.2.11 Quality Assurance Audit Samples. When making compliance
determinations, and upon availability, audit samples may be obtained
from the appropriate EPA regional Office or from the responsible
enforcement authority.

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

8.0 Sample Collection, Preservation, Transport, and Storage

8.1 Sample Collection. A sample that is representative of the ore
lot to be tested must be taken prior to analysis. (A portion of the
samples routinely collected for metals analysis may be used provided
the sample is representative of the ore being tested.)
8.2 Sample Preparation. The sample must be ground into a finely
pulverized state.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
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.
------------------------------------------------------------------------

10.0 Calibration and Standardizations

Note: Maintain a laboratory log of all calibrations.

10.1 Preparation of Standard Solutions. Pipet 1, 5, 10, and 25 ml
of the stock As solution into separate 100-ml volumetric flasks. Add 10
ml KCl solution and dilute to the mark with 0.5 N HNO3. This
will give standard concentrations of 10, 50, 100, and 250 g
As/ml. For low-level arsenic samples that require the use of a graphite
furnace or vapor generator, follow the procedures in Section 11.3:1.
Dilute 10 ml of KCl solution to 100 ml with 0.5 N HNO3 and
use as a reagent blank.
10.2 Calibration Curve. Analyze the reagent blank and each
standard solution according to the procedures outlined in Section 11.3.
Repeat this procedure on each standard solution until two consecutive
peaks agree within 3 percent of their average value. 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 each standard solution. If the blank absorbance is greater than 2
percent of full-scale, the probable cause is Hg contamination of a
reagent or carry-over of As from a previous sample. Prepare the
calibration curve by plotting the corrected peak height of each
standard solution versus the corresponding final total As weight in the
solution.
10.3 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 must be less than 7 percent for
all standards.

11.0 Analytical Procedure

11.1 Sample Preparation. Weigh 50 to 500 mg of finely pulverized
sample to the nearest 0.1 mg. Transfer the sample into the Teflon cup
of the digestion bomb, and add 2 ml each of concentrated
HNO3 and HF. Seal the bomb immediately to prevent the loss
of any volatile arsenic compounds that may form. Heat in an oven at 105
deg.C (221 deg.F) for 2 hours. Remove the bomb from the oven and
allow to cool. Using a Teflon filter, quantitatively filter the
digested sample into a 50-ml polypropylene volumetric flask. Rinse the
bomb three times with small portions of 0.5 N HNO3, and
filter the rinses into the flask. Add 5 ml of KCl solution to the
flask, and dilute to 50 ml with 0.5 N HNO3.
11.2 Spectrophotometer Preparation.
11.2.1 Turn on the power; set the wavelength, slit width, and lamp
current. 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.
11.2.2 Develop a spectrophotometer calibration curve as outlined
in Sections 10.2 and 10.3.
11.3 Arsenic Determination. Analyze an appropriately sized aliquot
of each diluted sample (from Section 11.1) until two consecutive peak
heights agree within 3 percent of their average value. If applicable,
follow the procedures outlined in Section 11.3.1. If the sample
concentration falls outside the range of the calibration curve, make an
appropriate dilution with 0.5 N HNO3 so that the final
concentration falls within the range of the curve. Using the
calibration curve, determine the As concentration in each sample.

Note: Because instruments vary between manufacturers, no
detailed operating instructions will be given here. Instead, the
instrument manufacturer's detailed operating instructions should be
followed.

11.3.1 Arsenic Determination at Low Concentration. The lower limit
of flame AAS is 10 g As/ml. If the arsenic concentration of
any sample is at a lower level, use the vapor generator or graphite
furnace which is available as

[[Page 62205]]

an accessory component. Flame, graphite furnace, or vapor generators
may be used for samples whose concentrations are between 10 and 30
g/ml. Follow the manufacturer's instructions in the use of
such equipment.
11.3.1.1 Vapor Generator Procedure. Place a sample containing
between 0 and 5 g of arsenic in the reaction tube, and dilute
to 15 ml with water. Since there is some trial and error involved in
this procedure, it may be necessary to screen the samples by
conventional AAS until an approximate concentration is determined.
After determining the approximate concentration, adjust the volume of
the sample accordingly. Pipet 15 ml of concentrated HCl into each tube.
Add 1 ml of 30 percent KI solution. Place the reaction tube into a 50
deg.C (120 deg.F) water bath for 5 minutes. Cool to room temperature.
Connect the reaction tube to the vapor generator assembly. When the
instrument response has returned to baseline, inject 5.0 ml of 5
percent NaBH4 and integrate the resulting spectrophotometer
signal over a 30-second time period.
11.3.1.2 Graphite Furnace Procedure. Pipet 5 ml of the digested
solution into a 10-ml volumetric flask. Add 1 ml of the 1 percent
nickel nitrate solution, 0.5 ml of 50 percent HNO3, and 1 ml
of the 3 percent H2O2, and dilute to 10 ml with
water. The sample is now ready to inject in the furnace for analysis.
11.4 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 average
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 Mandatory Check for Matrix Effects on the Arsenic Results.
Same as Method 12, Section 11.5.
11.6 Audit Sample Analysis.
11.6.1 When the method is used to analyze samples to demonstrate
compliance with a source emission regulation, a set of EPA audit
samples must be analyzed, subject to availability.
11.6.2 Concurrently analyze the audit samples and the compliance
samples in the same manner to evaluate the technique of the analyst and
the standards preparation.

11.6.3 The same analyst, analytical reagents, and analytical
system shall be used for the compliance samples and the EPA audit
samples. If this condition is met, duplicate auditing of subsequent
compliance analyses for the same enforcement agency within a 30-day
period is waived. An audit sample set may not be used to validate
different sets of compliance samples under the jurisdiction of separate
enforcement agencies, unless prior arrangements have been made with
both enforcement agencies.
11.7 Audit Sample Results.
11.7.1 Calculate the audit sample concentrations in g/m\3\ and
submit results using the instructions provided with the audit samples.
11.7.2 Report the results of the audit samples and the compliance
determination samples along with their identification numbers, and the
analyst's name to the responsible enforcement authority. Include this
information with reports of any subsequent compliance analyses for the
same enforcement authority during the 30-day period.
11.7.3 The concentrations of the audit samples obtained by the
analyst shall agree within 10 percent of the actual concentrations. If
the 10 percent specification is not met, reanalyze the compliance and
audit samples, and include initial and reanalysis values in the test
report.
11.7.4 Failure to meet the 10 percent specification may require
retests until the audit problems are resolved. However, if the audit
results do not affect the compliance or noncompliance status of the
affected facility, the Administrator may waive the reanalysis
requirement, further audits, or retests and accept the results of the
compliance test. While steps are being taken to resolve audit analysis
problems, the Administrator may also choose to use the data to
determine the compliance or noncompliance status of the affected
facility.

12.0 Data Analysis and Calculations

12.1 Calculate the percent arsenic in the ore sample as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.524

Where:

Ca = Concentration of As as read from the standard curve,
g/ml.
Fd = Dilution factor (equals to 1 if the sample has not been
diluted).
W = Weight of ore sample analyzed, mg.
5 = (50 ml sample `` 100)/(103 g/mg).

13.0 Method Performance

13.1 Sensitivity. The lower limit of flame AAS is 10 g
As/ml. The analytical procedure includes provisions for the use of a
graphite furnace or vapor generator for samples with a lower arsenic
concentration.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

Same as References 1 through 9 of Section 17.0 of Method 5, with
the addition of the following:

1. Perkin Elmer Corporation. Analytical Methods of Atomic
Absorption Spectrophotometry. 303-0152. Norwalk, Connecticut.
September 1976. pp 5-6.
2. Ringwald, D. Arsenic Determination on Process Materials from
ASARCO's Copper Smelter in Tacoma, Washington. Unpublished Report.
Prepared for Emission Measurement Branch, Emission Standards and
Engineering Division, U.S. Environmental Protection Agency, Research
Triangle Park, North Carolina. August 1980. 35 pp.
3. Stack Sampling Safety Manual (Draft). U.S. Environmental
Protection Agency, Office of Air Quality Planning and Standard,
Research Triangle Park, NC. September 1978.

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

Method 108B--Determination of Arsenic Content in Ore Samples From
Nonferrous Smelters

[[Page 62206]]

obtain reliable results, persons using this method should have a
thorough knowledge of at least the following additional test
methods: Method 12 and Method 108A.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Arsenic compounds as arsenic 7440-38-2........ Lower limit 10 g/ml.
------------------------------------------------------------------------

1.2 Applicability. This method applies to the determination of
inorganic As content of process ore and reverberatory matte samples
from nonferrous smelters and other sources as specified in an
applicable subpart of the regulations. Samples resulting in an
analytical concentration greater than 10 g As/ml may be
analyzed by this method. For lower level arsenic samples, Method 108C
should be used.
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

Arsenic bound in ore samples is liberated by acid digestion and
analyzed by flame atomic absorption spectrophotometry (AAS).

3.0 Definitions [Reserved]

4.0 Interferences

5.0 Safety

5.1 Disclaimer. This method may involve hazardous materials,
operations, and equipment. This test method may not address all of the
safety problems associated with its use. It is the responsibility of
the user 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 that prevent chemical
splashes are recommended. 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 corrosive liquid with toxic
vapors. Vapors are highly irritating to eyes, skin, nose, and lungs,
causing severe damage. May cause bronchitis, pneumonia, or edema of
lungs. Exposure to concentrations of 0.13 to 0.2 percent can be lethal
to humans in a few minutes. Provide ventilation to limit exposure.
Reacts with metals, producing hydrogen gas.
5.2.2 Hydrofluoric Acid (HF). Highly corrosive to eyes, skin,
nose, throat, and lungs. Reaction to exposure may be delayed by 24
hours or more. Provide ventilation to limit exposure.
5.2.3 Nitric Acid (HNO3). Highly corrosive to eyes,
skin, nose, and lungs. Vapors are highly toxic and can 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.
5.2.4 Perchloric Acid (HClO4). Corrosive to eyes, skin,
nose, and throat. Provide ventilation to limit exposure. Very strong
oxidizer. Keep separate from water and oxidizable materials to prevent
vigorous evolution of heat, spontaneous combustion, or explosion. Heat
solutions containing HClO4 only in hoods specifically
designed for HClO4.

6.0 Equipment and Supplies

6.1 Sample Preparation. The following items are required for
sample preparation:
6.1.1 Teflon Beakers. 150-ml.
6.1.2 Graduated Pipets. 5-ml disposable.
6.1.3 Graduated Cylinder. 50-ml.
6.1.4 Volumetric Flask. 100-ml.
6.1.5 Analytical Balance. To measure within 0.1 mg.
6.1.6 Hot Plate.
6.1.7 Perchloric Acid Fume Hood.
6.2 Analysis. The following items are required for analysis:
6.2.1 Spectrophotometer. Equipped with an electrodeless discharge
lamp and a background corrector to measure absorbance at 193.7 nm.
6.2.2 Beaker and Watch Glass. 400-ml.
6.2.3 Volumetric Flask. 1-liter.
6.2.4 Volumetric Pipets. 1-, 5-, 10-, and 25-ml.

7.0 Reagents and Standards

8.0 Sample Collection, Preservation, Transport, and Storage

Same as in Method 108A, Sections 8.1 and 8.2.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.2.......................... Spectrophotometer Ensure linearity of
calibration. spectrophotometer
response to
standards.

[[Page 62207]]

11.4.......................... Check for matrix Eliminate matrix
effects. effects.
11.5.......................... Audit sample Evaluate analyst's
analysis. technique and
standards
preparation.
------------------------------------------------------------------------

10.0 Calibration and Standardization

Note: Maintain a laboratory log of all calibrations.

10.1 Preparation of Standard Solutions. Pipet 1, 5, 10, and 25 ml
of the stock As solution into separate 100-ml volumetric flasks. Add 2
ml of HClO4, 10 ml of HCl, and dilute to the mark with
water. This will provide standard concentrations of 10, 50, 100, and
250 g As/ml.
10.2 Calibration Curve and Spectrophotometer Calibration Quality
Control. Same as Method 108A, Sections 10.2 and 10.3

11.0 Analytical Procedure

11.1 Sample Preparation. Weigh 100 to 1000 mg of finely pulverized
sample to the nearest 0.1 mg. Transfer the sample to a 150-ml Teflon
beaker. Dissolve the sample by adding 15 ml of HNO3, 10 ml
of HCl, 10 ml of HF, and 10 ml of HClO4 in the exact order
as described, and let stand for 10 minutes. In a HClO4 fume
hood, heat on a hot plate until 2-3 ml of HClO4 remain, then
cool. Add 20 ml of water and 10 ml of HCl. Cover and warm until the
soluble salts are in solution. Cool, and transfer quantitatively to a
100-ml volumetric flask. Dilute to the mark with water.
11.2 Spectrophotometer Preparation. Same as in Method 108A,
Section 11.2.
11.3 Arsenic Determination. If the sample concentration falls
outside the range of the calibration curve, make an appropriate
dilution with 2 percent HClO4/10 percent HCl (prepared by
diluting 2 ml concentrated HClO4 and 10 ml concentrated HCl
to 100 ml with water) so that the final concentration falls within the
range of the curve. Using the calibration curve, determine the As
concentration in each sample.

Note: Because instruments vary between manufacturers, no
detailed operating instructions will be given here. Instead, the
instrument manufacturer's detailed operating instructions should be
followed.

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 average
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.
11.4 Mandatory Check for Matrix Effects on the Arsenic Results.
Same as Method 12, Section 11.5.
11.5 Audit Sample Analysis. Same as in Method 108A, Section 11.6.

12.0 Data Analysis and Calculations

Same as in Method 108A, Section 12.0.

13.0 Method Performance

13.1 Sensitivity. The lower limit of flame AAS is 10 g
As/ml.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as in Method 108A, Section 16.0.

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

Method 108C--Determination of Arsenic Content in Ore Samples From
Nonferrous Smelters (Molybdenum Blue Photometric Procedure)

Note: This method does not include all of the specifications
(e.g., equipment and supplies) and procedures (e.g., sampling and
analytical) essential to its performance. Some material is
incorporated by reference from other methods in this part.
Therefore, to obtain reliable results, persons using this method
should have a thorough knowledge of at least Method 108A.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Arsenic compounds as arsenic 7440-38-2........ Lower limit 0.0002
(As). percent As by
weight.
------------------------------------------------------------------------

2.0 Summary of Method

Arsenic bound in ore samples is liberated by acid digestion and
analyzed by the molybdenum blue photometric procedure.

3.0 Definitions. [Reserved]

4.0 Interferences. [Reserved]

5.0 Safety

[[Page 62208]]

5.2.3 Nitric Acid (HNO4). Highly corrosive to eyes,
skin, nose, and lungs. Vapors are highly toxic and can 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.
5.2.4 Perchloric Acid (HClO4). Corrosive to eyes, skin,
nose, and throat. Provide ventilation to limit exposure. Very strong
oxidizer. Keep separate from water and oxidizable materials to prevent
vigorous evolution of heat, spontaneous combustion, or explosion. Heat
solutions containing HClO4 only in hoods specifically
designed for HClO4.
5.2.5 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.

6.0 Equipment and Supplies

6.1 Sample Preparation. The following items are required for
sample preparation:
6.1.1 Analytical Balance. To measure to within 0.1 mg.
6.1.2 Erlenmeyer Flask. 300-ml.
6.1.3 Hot Plate.
6.1.4 Distillation Apparatus. No. 6, in ASTM E 50-82, 86, or 90
(Reapproved 1995)(incorporated by reference--see Sec. 61.18); detailed
in Figure 108C-1.
6.1.5 Graduated Cylinder. 50-ml.
6.1.6 Perchloric Acid Fume Hood.
6.2 Analysis. The following items are required for analysis:
6.2.1 Spectrophotometer. Capable of measuring at 660 nm.

6.2.2 Volumetric Flasks. 50- and 100-ml.

7.0 Reagents and Standards

8.0 Sample Collection, Preservation, Transport, and Storage

Same as in Method 108A, Sections 8.1 and 8.2.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.2.......................... Calibration curve Ensure linearity of
preparation. spectrophotometric
analysis of
standards.
11.3.......................... Audit sample Evaluate analyst's
analysis. technique and
standards
preparation.
------------------------------------------------------------------------

10.0 Calibration and Standardizations

Note: Maintain a laboratory log of all calibrations.

10.1 Preparation of Standard Solutions. Transfer 1.0, 2.0, 4.0,
8.0, 12.0, 16.0, and 20.0 ml of standard arsenic solution (10
g/ml) to each of seven 50-ml volumetric flasks. Dilute to 20
ml with dilute HCl. Add one drop of methyl orange solution and
neutralize to the yellow color with dropwise addition of
NH4OH. Just bring back to the red color by dropwise addition
of dilute HCl, and add 10 ml in excess. Proceed with the color
development as described in Section 11.2.
10.2 Calibration Curve. Plot the spectrophotometric readings of
the calibration solutions against g As per 50 ml of solution.
Use this curve to determine the As concentration of each sample.
10.3 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 must be less than 7 percent for
all standards.

11.0 Analytical Procedure

11.1 Sample Preparation.
11.1.1 Weigh 1.0 g of finely pulverized sample to the nearest 0.1
mg. Transfer the sample to a 300 ml Erlenmeyer flask and add 15 ml of
HNO3, 4 ml HCl, 2 ml HF, 3 ml HClO4, and 15 ml
H2SO4, in the order listed. In a HClO4
fume hood, heat on a hot plate to decompose the sample. Then heat while
swirling over an open flame until dense white fumes evolve. Cool, add
15

[[Page 62209]]

ml of water, swirl to hydrate the H2SO4
completely, and add several boiling granules. Cool to room temperature.
11.1.2 Add 1 g of KBr, 1 g hydrazine sulfate, and 50 ml HCl.
Immediately attach the distillation head with thermometer and dip the
side arm into a 50-ml graduated cylinder containing 25 ml of water and
2 ml of bromine water. Keep the graduated cylinder immersed in a beaker
of cold water during distillation. Distill until the temperature of the
vapor in the flask reaches 107 deg.C (225 deg.F). When distillation
is complete, remove the flask from the hot plate, and simultaneously
wash down the side arm with water as it is removed from the cylinder.
11.1.3 If the expected arsenic content is in the range of 0.0020
to 0.10 percent, dilute the distillate to the 50-ml mark of the
cylinder with water, stopper, and mix. Transfer a 5.0-ml aliquot to a
50-ml volumetric flask. Add 10 ml of water and a boiling granule. Place
the flask on a hot plate, and heat gently until the bromine is expelled
and the color of methyl orange indicator persists upon the addition of
1 to 2 drops. Cool the flask to room temperature. Neutralize just to
the yellow color of the indicator with dropwise additions of
NH4OH. Bring back to the red color by dropwise addition of
dilute HCl, and add 10 ml excess. Proceed with the molybdenum blue
color development as described in Section 11.2.
11.1.4 If the expected arsenic content is in the range of 0.0002
to 0.0010 percent As, transfer either the entire initial distillate or
the measured remaining distillate from Section 11.1.2 to a 250-ml
beaker. Wash the cylinder with two successive portions of concentrated
HNO3, adding each portion to the distillate in the beaker.
Add 4 ml of concentrated HClO4, a boiling granule, and cover
with a flat watch glass placed slightly to one side. Boil gently on a
hot plate until the volume is reduced to approximately 10 ml. Add 3 ml
of HNO3, and continue the evaporation until HClO4
is refluxing on the beaker cover. Cool briefly, rinse the underside of
the watch glass and the inside of the beaker with about 3-5 ml of
water, cover, and continue the evaporation to expel all but 2 ml of the
HClO4.

Note: If the solution appears cloudy due to a small amount of
antimony distilling over, add 4 ml of 50 percent HCl and 5 ml of
water, cover, and warm gently until clear. If cloudiness persists,
add 5 ml of HNO3 and 2 ml H2SO4.
Continue the evaporation of volatile acids to solubilize the
antimony until dense white fumes of H2SO4
appear. Retain at least 1 ml of the H2SO4.

11.1.5 To the 2 ml of HClO4 solution or 1 ml of
H2SO4 solution, add 15 ml of water, boil gently
for 2 minutes, and then cool. Proceed with the molybdenum blue color
development by neutralizing the solution directly in the beaker just to
the yellow indicator color by dropwise addition of NH4OH.
Obtain the red color by dropwise addition of dilute HCl. Transfer the
solution to a 50-ml volumetric flask. Rinse the beaker successively
with 10 ml of dilute HCl, followed by several small portions of water.
At this point the volume of solution in the flask should be no more
than 40 ml. Continue with the color development as described in Section
11.2.
11.2 Analysis.
11.2.1 Add 1 ml of KBrO3 solution to the flask and heat
on a low-temperature hot plate to about 50 deg.C (122 deg.F) to
oxidize the arsenic and methyl orange. Add 5.0 ml of ammonium molybdate
solution to the warm solution and mix. Add 2.0 ml of hydrazine sulfate
solution, dilute until the solution comes within the neck of the flask,
and mix. Place the flask in a 400 ml beaker, 80 percent full of boiling
water, for 10 minutes. Enough heat must be supplied to prevent the
water bath from cooling much below the boiling point upon inserting the
volumetric flask. Remove the flask, cool to room temperature, dilute to
the mark, and mix.
11.2.2 Transfer a suitable portion of the reference solution to an
absorption cell, and adjust the spectrophotometer to the initial
setting using a light band centered at 660 nm. While maintaining this
spectrophotometer adjustment, take the readings of the calibration
solutions followed by the samples.
11.3 Audit Sample Analysis. Same as in Method 108A, Section 11.6.

12.0 Data Analysis and Calculations

Same as in Method 108A, Section 12.0.

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. Ringwald, D. Arsenic Determination on Process Materials from
ASARCO's Copper Smelter in Tacoma, Washington. Unpublished Report.
Prepared for the Emission Measurement Branch, Technical Support
Division, U.S. Environmental Protection Agency, Research Triangle
Park, North Carolina. August 1980. 35 pp.
BILLING CODE 6560-50-P

[[Page 62210]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.525

BILLING CODE 6560-50-C

Method 111--Determination of Polonium-210 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.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Polonium...................... 7440-08-6........ Not specified.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of the polonium-210 content of particulate matter samples collected
from stationary source exhaust stacks, and for the use of these data to
calculate polonium-210 emissions from individual sources and from all
affected sources at a facility.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

A particulate matter sample, collected according to Method 5, is
analyzed for polonium-210 content: the polonium-210 in the sample is
put in solution, deposited on a metal disc, and the radioactive
disintegration rate measured. Polonium in acid solution spontaneously
deposits on surfaces of metals that are more electropositive than
polonium. This principle is routinely used in the radiochemical
analysis of polonium-210. Data reduction procedures are provided,
allowing the calculation of polonium-210 emissions from individual
sources

[[Page 62211]]

and from all affected sources at a facility, using data obtained from
Methods 2 and 5 and from the analytical procedures herein.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

5.1 Disclaimer. This method may involve hazardous materials,
operations, and equipment. This test method 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 at least 15 minutes. Remove clothing under
shower and decontaminate. Treat residual chemical burns as thermal
burns.
5.2.1 Hydrochloric Acid (HCl). Highly corrosive liquid with toxic
vapors. Vapors are highly irritating to eyes, skin, nose, and lungs,
causing severe damage. May cause bronchitis, pneumonia, or edema of
lungs. Exposure to concentrations of 0.13 to 0.2 percent can be lethal
to humans in a few minutes. Provide ventilation to limit exposure.
Reacts with metals, producing hydrogen gas.
5.2.2 Hydrofluoric Acid (HF). Highly corrosive to eyes, skin,
nose, throat, and lungs. Reaction to exposure may be delayed by 24
hours or more. Provide ventilation to limit exposure.
5.2.3 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.
5.2.4 Perchloric Acid (HClO4). Corrosive to eyes, skin,
nose, and throat. Provide ventilation to limit exposure. Keep separate
from water and oxidizable materials to prevent vigorous evolution of
heat, spontaneous combustion, or explosion. Heat solutions containing
HClO4 only in hoods specifically designed for
HClO4.

6.0 Equipment and Supplies

6.1 Alpha Spectrometry System. Consisting of a multichannel
analyzer, biasing electronics, silicon surface barrier detector, vacuum
pump and chamber.
6.2 Constant Temperature Bath at 85 deg.C (185 deg.F).
6.3 Polished Silver Discs. 3.8 cm diameter, 0.4 mm thick with a
small hole near the edge.
6.4 Glass Beakers. 400 ml, 150 ml.
6.5 Hot Plate, Electric.
6.6 Fume Hood.
6.7 Teflon Beakers, 150 ml.
6.8 Magnetic Stirrer.
6.9 Stirring Bar.
6.10 Hooks. Plastic or glass, to suspend plating discs.
6.11 Internal Proportional Counter. For measuring alpha particles.
6.12 Nucleopore Filter Membranes. 25 mm diameter, 0.2 micrometer
pore size or equivalent.
6.13 Planchets. Stainless steel, 32 mm diameter with 1.5 mm lip.
6.14 Transparent Plastic Tape. 2.5 cm wide with adhesive on both
sides.
6.15 Epoxy Spray Enamel.
6.16 Suction Filter Apparatus. For 25 mm diameter filter.
6.17 Wash Bottles, 250 ml capacity.
6.18 Graduated Cylinder, plastic, 25 ml capacity.
6.19 Volumetric Flasks, 100 ml, 250 ml.

7.0 Reagents and Standards

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

9.0 Quality Control

9.1 General Requirement.
9.1.1 All analysts using this method are required to demonstrate
their ability to use the method and to define their respective accuracy
and precision criteria.
9.2 Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.1.......................... Standardization Ensure precision of
of alpha sample analyses.
spectrometry
system.
10.3.......................... Standardization Ensure precise sizing
of internal of sample aliquot.
proportional
counter.
11.1, 11.2.................... Determination of Minimize background
procedure effects.
background and
instrument
background.
11.3.......................... Audit sample Evaluate analyst's
analysis. technique.
------------------------------------------------------------------------

10.0 Calibration and Standardization

10.1 Standardization of Alpha Spectrometry System.
10.1.1 Add a quantity of the actinide standard solution to a 100
ml volumetric flask so that the final concentration when diluted to a
volume of 100 ml will be approximately 1 pCi/ml.
10.1.2 Add 10 ml of 16 M HNO3 and dilute to 100 ml with
water.
10.1.3 Add 20 ml of 1 M HCl to each of six 150 ml beakers. Add 1.0
ml of lanthanum carrier, 0.1 mg lanthanum per ml, to the acid solution
in each beaker.
10.1.4 Add 1.0 ml of the 1 pCi/ml working solution (from Section
10.1.1)

[[Page 62212]]

to each beaker. Add 5.0 ml of 3 M HF to each beaker.
10.1.5 Cover beakers and allow solutions to stand for a minimum of
30 minutes. Filter the contents of each beaker through a separate
filter membrane using the suction filter apparatus. After each
filtration, wash the filter membrane with 10 ml of distilled water and
5 ml of ethanol, and allow the filter membrane to air dry on the filter
apparatus.
10.1.6 Carefully remove the filter membrane and mount it,
filtration side up, with double-side tape on the inner surface of a
planchet. Place planchet in an alpha spectrometry system and count each
planchet for 1000 minutes.
10.1.7 Calculate the counting efficiency of the detector for each
aliquot of the 1 pCi/ml actinide working solution using Eq. 111-1 in
Section 12.2.
10.1.8 Determine the average counting efficiency of the detector,
Ec, by calculating the average of the six determinations.
10.2 Preparation of Standardized Solution of Polonium-209.
10.2.1 Add a quantity of the Po-209 solution to a 100 ml
volumetric flask so that the final concentration when diluted to a 100
ml volume will be approximately 1 pCi/ml.
10.2.2 Follow the procedures outlined in Sections 10.1.2 through
10.1.6, except substitute 1.0 ml of polonium-209 tracer solution
(Section 10.2.1) and 3.0 ml of 15 M ammonium hydroxide for the 1 pCi/ml
actinide working solution and the 3 M HF, respectively.
10.2.3 Calculate the activity of each aliquot of the polonium-209
tracer solution using Eq. 111-2 in Section 12.3.
10.2.4 Determine the average activity of the polonium-209 tracer
solution, F, by averaging the results of the six determinations.
10.3 Standardization of Internal Proportional Counter
10.3.1 Add a quantity of the actinide standard solution to a 100
ml volumetric flask so that the final concentration when diluted to a
100 ml volume will be approximately 100 pCi/ml.
10.3.2 Follow the procedures outlined in Sections 10.1.2 through
10.1.6, except substitute the 100 pCi/ml actinide working solution for
the 1 pCi/ml solution, place the planchet in an internal proportional
counter (instead of an alpha spectrometry system), and count for 100
minutes (instead of 1000 minutes).
10.3.3 Calculate the counting efficiency of the internal
proportional counter for each aliquot of the 100 pCi/ml actinide
working solution using Eq. 111-3 in 12.4.
10.3.4 Determine the average counting efficiency of the internal
proportional counter, EI, by averaging the results of the
six determinations.

11.0 Analytical Procedure

Note: Perform duplicate analyses of all samples, including
background counts, quality assurance audit samples, and Method 5
samples. Duplicate measurements are considered acceptable when the
difference between them is less than two standard deviations as
described in EPA 600/4-77-001 or subsequent revisions.

11.1 Determination of Procedure Background. Background counts used
in all equations are determined by performing the specific analysis
required using the analytical reagents only. All procedure background
counts and sample counts for the internal proportional counter should
utilize a counting time of 100 minutes; for the alpha spectrometry
system, 1000 minutes. These background counts should be performed no
less frequently than once per 10 sample analyses.
11.2 Determination of Instrument Background. Instrument
backgrounds of the internal proportional counter and the alpha
spectrometry system should be determined on a weekly basis. Instrument
background should not exceed procedure background. If this occurs, it
may be due to a malfunction or contamination, and should be corrected
before use.
11.3 Quality Assurance Audit Samples. An externally prepared
performance evaluation sample shall be analyzed no less frequently than
once per 10 sample analyses, and the results reported with the test
results.
11.4 Sample Preparation. Treat the Method 5 samples [i.e., the
glass fiber filter (Container No. 1) and the acetone rinse (Container
No. 2)] as follows:
11.4.1 Container No. 1. Transfer the filter and any loose
particulate matter from the sample container to a 150-ml Teflon beaker.
11.4.2 Container No. 2. Note the level of liquid in the container,
and confirm on the analysis sheet whether leakage occurred during
transport. If a noticeable amount of leakage has occurred, either void
the sample or use methods, subject to the approval of the
Administrator, to correct the final results. Transfer the contents to a
400-ml glass beaker. Add polonium-209 tracer solution to the glass
beaker in an amount approximately equal to the amount of polonium-210
expected in the total particulate sample. Record the activity of the
tracer solution added. Add 16 M nitric acid to the beaker to digest and
loosen the residue.
11.4.3 Transfer the contents of the glass beaker to the Teflon
beaker containing the glass fiber filter. Rinse the glass beaker with
16 M HNO3. If necessary, reduce the volume in the beaker by
evaporation until all of the nitric acid HNO3 from the glass
beaker has been transferred to the Teflon beaker.
11.4.4 Add 30 ml of 29 M HF to the Teflon beaker and evaporate to
near dryness on a hot plate in a properly operating hood.

Note: Do not allow the residue to go to dryness and overheat;
this will result in loss of polonium.

11.4.5 Repeat step 11.4.4 until the filter is dissolved.
11.4.6 Add 100 ml of 16 M HNO3 to the residue in the
Teflon beaker and evaporate to near dryness.

Note: Do not allow the residue to go to dryness.

11.4.7 Add 50 ml of 16 M HNO3 and 10 ml of 12 M
perchloric acid to the Teflon beaker and heat until dense fumes of
perchloric acid are evolved.
11.4.8 Repeat steps 11.4.4 to 11.4.7 as necessary until sample is
completely dissolved.
11.4.9 Add 10 ml of 12 M HCl to the Teflon beaker and evaporate to
dryness. Repeat additions and evaporations several times.
11.4.10 Transfer the sample to a 250-ml volumetric flask and
dilute to volume with 3 M HCl.
11.5 Sample Screening. To avoid contamination of the alpha
spectrometry system, check each sample as follows:
11.5.1 Add 20 ml of 1 M HCl, 1 ml of the lanthanum carrier
solution (0.1 mg La/ml), a 1 ml aliquot of the sample solution from
Section 11.4.10, and 3 ml of 15 M ammonium hydroxide to a 250-ml beaker
in the order listed. Allow this solution to stand for a minimum of 30
minutes.
11.5.2 Filter the solution through a filter membrane using the
suction filter apparatus. Wash the filter membrane with 10 ml of water
and 5 ml of ethanol, and allow the filter membrane to air dry on the
filter apparatus.
11.5.3 Carefully remove the filter membrane and mount it,
filtration side up, with double-side tape on the inner surface of a
planchet. Place the planchet in an internal proportional counter, and
count for 100 minutes.
11.5.4 Calculate the activity of the sample using Eq. 111-4 in
Section 12.5.
11.5.5 Determine the aliquot volume of the sample solution from
Section 11.4.10 to be analyzed for polonium-210, such that the aliquot
contains an

[[Page 62213]]

activity between 1 and 4 picocuries. Use Eq. 111-5 in Section 12.6.
11.6 Preparation of Silver Disc for Spontaneous Electrodeposition.
11.6.1 Clean both sides of the polished silver disc with silver
cleaner and with degreaser.
11.6.2 Place disc on absorbent paper and spray one side with epoxy
spray enamel. This should be carried out in a well-ventilated area,
with the disc lying flat to keep paint on one side only. Allow paint to
dry for 24 hours before using disc for deposition.
11.7 Sample Analysis.
11.7.1 Add the aliquot of sample solution from Section 11.4.10 to
be analyzed for polonium-210, the volume of which was determined in
Section 11.5.5, to a suitable 200-ml container to be placed in a
constant temperature bath.

Note: Aliquot volume may require a larger container.

11.7.2 If necessary, bring the volume to 100 ml with 1 M HCl. If
the aliquot volume exceeds 100 ml, use total aliquot.
11.7.3 Add 200 mg of ascorbic acid and heat solution to 85 deg.C
(185 deg.F) in a constant temperature bath.
11.7.4 Suspend a silver disc in the heated solution using a glass
or plastic rod with a hook inserted through the hole in the disc. The
disc should be totally immersed in the solution, and the solution must
be stirred constantly, at all times during the plating operation.
Maintain the disc in solution for 3 hours.
11.7.5 Remove the silver disc, rinse with deionized distilled
water, and allow to air dry at room temperature.
11.7.6 Place the disc, with deposition side (unpainted side) up,
on a planchet and secure with double-side plastic tape. Place the
planchet with disc in alpha spectrometry system and count for 1000
minutes.

12.0 Data Analysis and Calculations.

12.1 Nomenclature.

A = Picocuries of polonium-210 in the Method 5 sample (from Section
12.8).
AA = Picocuries of actinide added.
AL = Volume of sample aliquot used, in ml (specified in
Section 11.5.1 as 1 ml).
AS = Aliquot to be analyzed, in ml.
BB = Procedure background counts measured in polonium-209
spectral region.
BT = Polonium-209 tracer counts in sample.
CT = Total counts in polonium-210 spectral region.
D = Decay correction for time ``t'' (in days) from sample collection to
sample counting, given by: D=e-0.005t
EC = Average counting efficiency of detector (from Section
10.1.8), as counts per disintegration.
ECi = Counting efficiency of the detector for aliquot i of
the actinide working solution, counts per disintegration.
EI = Average counting efficiency of the internal
proportional counter, as determined in Section 10.3.4, counts per
disintegration.
EIi = Counting efficiency of the internal proportional
counter for aliquot i of the 100 pCi/ml actinide working solution,
counts per disintegration.
EY = The fraction of polonium-209 recovered on the planchet
(from Section 12.7).
F= Average activity of polonium-209 in sample (from Section 10.2.4), in
pCi.
Fi = activity of aliquot i of the polonium-209 tracer
solution, in pCi.
L = Dilution factor (unitless). This is the volume of sample solution
prepared (specified as 250 ml in Section 11.1.10) divided by the volume
of the aliquot of sample solution analyzed for polonium-210 (from
Section 11.7.1).
Mi = Phosphorous rock processing rate of the source being
tested, during run i, Mg/hr.
Mk = Phosphate rock processed annually by source k, in Mg/
yr.
n = Number of calciners at the elemental phosphorus plant.
P = Total activity of sample solution from Section 11.4.10, in pCi (see
Eq. 111-4).
Qsd = Volumetric flow rate of effluent stream, as determined
by Method 2, in dscm/hr.
S = Annual polonium-210 emissions from the entire facility, in curies/
yr.
Vm(std) = Volume of air sample, as determined by Method 5,
in dscm.
Xk = Emission rate from source k, from Section 12.10, in
curies/Mg.
10-12 = Curies per picocurie.
2.22 = Disintegrations per minute per picocurie.
250 = Volume of solution from Section 11.4.10, in ml.

12.2 Counting Efficiency. Calculate the counting efficiency of the
detector for each aliquot of the 1 pCi/ml actinide working solution
using Eq. 111-1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.526

Where:

CB = Background counts in same peak area as CS.
CS = Gross counts in actinide peak.
T = Counting time in minutes, specified in Section 10.1.6 as 1000
minutes.

12.3 Polonium-209 Tracer Solution Activity. Calculate the activity
of each aliquot of the polonium-209 tracer solution using Eq. 111-2.
[GRAPHIC] [TIFF OMITTED] TR17OC00.527

Where:

CB = Background counts in the 4.88 MeV region of spectrum
the in the counting time T.
CS = Gross counts of polonium-209 in the 4.88 MeV region of
the spectrum in the counting time T.
T = Counting time, specified in Section 10.1.6 as 1000 minutes.

12.4 Control Efficiency of Internal Proportional Counter. Calculate
the counting efficiency of the internal proportional counter for each
aliquot of the 100 pCi/ml actinide working solution using Eq. 111-3.

[[Page 62214]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.528

Where:

CB = Gross counts of procedure background.
CS = Gross counts of standard.
T = Counting time in minutes, specified in Section 10.3.2 as 100
minutes.

12.5 Calculate the activity of the sample using Eq. 111-4.
[GRAPHIC] [TIFF OMITTED] TR17OC00.529

Where:

CB = Total counts of procedure background. (See Section
11.1).
CS = Total counts of screening sample.
T = Counting time for sample and background (which must be equal), in
minutes (specified in Section 11.5.3 as 100 minutes).

12.6 Aliquot Volume. Determine the aliquot volume of the sample
solution from Section 11.4.10 to be analyzed for polonium-210 , such
that the aliquot contains an activity between 1 and 4 picocuries using
Eq. 111-5.
[GRAPHIC] [TIFF OMITTED] TR17OC00.530

12.7 Polonium-209 Recovery. Calculate the fraction of polonium-209
recovered on the planchet, EY, using Eq. 111-6.
[GRAPHIC] [TIFF OMITTED] TR17OC00.531

Where:

T = Counting time, specified in Section 11.1 as 1000 minutes.

12.8 Polonium-210 Activity. Calculate the activity of polonium-210
in the Method 5 sample (including glass fiber filter and acetone rinse)
using Eq. 111-7.
[GRAPHIC] [TIFF OMITTED] TR17OC00.532

Where:

CB = Procedure background counts in polonium-210 spectral
region.
T = Counting time, specified in Section 11.1 as 1000 minutes for all
alpha spectrometry sample and background counts.

12.9 Emission Rate from Each Stack.
12.9.1 For each test run, i, on a stack, calculate the measured
polonium-210 emission rate, RSi, using Eq. 111-8.
[GRAPHIC] [TIFF OMITTED] TR17OC00.533

12.9.2 Determine the average polonium-210 emission rate from the
stack, RS, by taking the sum of the measured emission rates
for all runs, and dividing by the number of runs performed.
12.9.3 Repeat steps 12.9.1 and 12.9.2 for each stack of each
calciner.
12.10 Emission Rate from Each Source. Determine the total
polonium-210 emission rate, Xk, from each source, k, by
taking the sum of the average emission rates from all stacks to which
the source exhausts.
12.11 Annual Polonium-210 Emission Rate from Entire Facility.
Determine the annual elemental phosphorus plant emissions of polonium-
210, S, using Eq. 111-9.
[GRAPHIC] [TIFF OMITTED] TR17OC00.534

[[Page 62215]]

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. Blanchard, R.L. ``Rapid Determination of Lead-210 and
Polonium-210 in Environmental Samples by Deposition on Nickel.''
Anal. Chem., 38:189, pp. 189-192. February 1966.

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

* * * * *

PART 63--NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS
FOR SOURCE CATEGORIES

1. The authority citation for Part 63 continues to read as follows:

Authority: 42 U.S.C. 7401 et seq.

Sec. 63.7 [Amended]

2. Amend Sec. 63.7 by revising paragraph (c)(4)(i) as follows:

Sec. 63.7 Performance testing requirements.

* * * * *
(c) * * *
(4)(i) Performance test method audit program. The owner or operator
shall analyze performance audit (PA) samples during each performance
test. The owner or operator shall request performance audit materials
45 days prior to the test date. Cylinder audit gases, if available,
must be obtained from the appropriate EPA Regional Office or from the
responsible enforcement authority and analyzed in conjunction with the
field samples.
* * * * *

Sec. 63.11 [Amended]

3. Amend Sec. 63.11 as follows:
a. The definition of ``Ci'' in paragraph (b)(6)(ii) is
amended by revising ``D1946-77'' to read ``D1946-77 or 90 (Reapproved
1994).''
b. The definition of ``Hi'' in paragraph (b)(6)(ii) is
amended by revising ``D2382-76'' to read ``D2382-76 or 88 or D4809-
95.''

Sec. 63.14 [Amended]

4. In Sec. 63.14, by revising paragraph (b) to read as follows:

Sec. 63.14 Incorporation by reference.

* * * * *
(b) 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 D523-89, Standard Test Method for Specular Gloss, IBR
approved for Sec. 63.782.
(2) ASTM D1193-77, 91, Standard Specification for Reagent Water,
IBR approved for Appendix A: Method 306, Sections 7.1.1 and 7.4.2.
(3) ASTM D1331-89, Standard Test Methods for Surface and
Interfacial Tension of Solutions of Surface Active Agents, IBR approved
for Appendix A: Method 306B, Sections 6.2, 11.1, and 12.2.2.
(4) ASTM D1475-90, Standard Test Method for Density of Paint,
Varnish Lacquer, and Related Products, IBR approved for Sec. 63.788,
Appendix A.
(5) ASTM D1946-77, 90, 94, Standard Method for Analysis of Reformed
Gas by Gas Chromatography, IBR approved for Sec. 63.11(b)(6).
(6) ASTM D2369-93, 95, Standard Test Method for Volatile Content of
Coatings, IBR approved for Sec. 63.788, Appendix A.
(7) ASTM D2382-76, 88, Heat of Combustion of Hydrocarbon Fuels by
Bomb Calorimeter (High-Precision Method), IBR approved for
Sec. 63.11(b)(6).
(8) ASTM D2879-83, 96, Test Method for Vapor Pressure-Temperature
Relationship and Initial Decomposition Temperature of Liquids by
Isoteniscope, IBR approved for Sec. 63.111 of Subpart G.
(9) ASTM D3257-93, Standard Test Methods for Aromatics in Mineral
Spirits by Gas Chromatography, IBR approved for Sec. 63.786(b).
(10) ASTM 3695-88, Standard Test Method for Volatile Alcohols in
Water by Direct Aqueous-Injection Gas Chromatography, IBR approved for
Sec. 63.365(e)(1) of Subpart O.
(11) ASTM D3792-91, Standard Method for Water Content of Water-
Reducible Paints by Direct Injection into a Gas Chromatograph, IBR
approved for Sec. 63.788, Appendix A.
(12) ASTM D3912-80, Standard Test Method for Chemical Resistance of
Coatings Used in Light-Water Nuclear Power Plants, IBR approved for
Sec. 63.782.
(13) ASTM D4017-90, 96a, Standard Test Method for Water in Paints
and Paint Materials by the Karl Fischer Titration Method, IBR approved
for Sec. 63.788, Appendix A.
(14) ASTM D4082-89, Standard Test Method for Effects of Gamma
Radiation on Coatings for Use in Light-Water Nuclear Power Plants, IBR
approved for Sec. 63.782.
(15) ASTM D4256-89, 94, Standard Test Method for Determination of
the Decontaminability of Coatings Used in Light-Water Nuclear Power
Plants, IBR approved for Sec. 63.782.
(16) ASTM D4809-95, Standard Test Method for Heat of Combustion of
Liquid Hydrocarbon Fuels by Bomb Calorimeter (Precision Method), IBR
approved for Sec. 63.11(b)(6).
(17) ASTM E180-93, Standard Practice for Determining the Precision
of ASTM Methods for Analysis and Testing of Industrial Chemicals, IBR
approved for Sec. 63.786(b).
(18) ASTM E260-91, 96, General Practice for Packed Column Gas
Chromatography, IBR approved for Secs. 63.750(b)(2) and 63.786(b)(5).

Sec. 63.111 [Amended]

5. In Sec. 63.111, paragraph (3) of the definition of the term
``Maximum true vapor pressure'' is amended by revising ``D2879-83'' to
read ``D2879-83 or 96.''

Sec. 63.301 [Amended]

6. Amend Sec. 63.301 as follows:
a. The definition of the term ``Foundry coke producer'' is amended
by revising the words ``1.25 million megagrams per year'' to read
``1.25 million megagrams per year (1.38 million tons per year).''
b. The definitions of the terms ``Short coke oven battery'' and
``Tall coke oven battery'' are amended by revising the words ``6
meters'' to read ``6 meters (20 feet)'' wherever they occur.

Sec. 63.304 [Amended]

7. In Sec. 63.304, paragraph (b)(6)(iii) is amended by revising the
words ``2.7 million Mg/yr'' to read ``2.7 million Mg/yr (3.0 million
ton/yr).''

Sec. 63.750 [Amended]

8. In Sec. 63.750, paragraph (b)(2) is amended by revising ``ASTM E
260-91 (incorporated by reference as specified in Sec. 63.14 of subpart
A of this part)'' to read ``ASTM E 260-91 or 96 (incorporated by
reference--see Sec. 63.14 of Subpart A of this part).''

Sec. 63.782 [Amended]

9. Amend Sec. 63.782 as follows:
a. The definition for ``High-gloss specialty coating'' is amended
by revising ``ASTM Method D523,'' to read ``ASTM D523-89.''
b. The definition for Nuclear specialty coating is amended by
revising ``ASTM D4256-89,'' to read ``ASTM D4256-89 or 94.''

Sec. 63.786 [Amended]

10. In Sec. 63.786, paragraph (b)(5) is amended by revising ``ASTM
Method E260-91'' to read ``ASTM E260-91 or 96.''

[[Page 62216]]

Sec. 63.788 [Amended]

11. In Sec. 63.788, the Appendix A to Subpart II of Part 63-VOC
Data Sheet is amended by revising ``ASTM Method D2369-93,'' and ``ASTM
D4017-90'' to read ``ASTM D2369-93 or 95'' and ``ASTM D4017-81, 90, or
96a'' respectively.

Appendix A--[Amended]

12. Amend Method 310B in Appendix A as follows:
a. Section 1.0 is amended by revising ``ethylidene norbornene
(ENB)'' to read ``Applicable Termonomer.''
b. Section 1.0 is amended by deleting ``16219-75-3.''
c. In Section 5.0, correcting the section numbering from ``5.1,
5.2, 5.3, 5.3, 5.4, 5.5, 5.6, and 5.7'' to ``5.1, 5.2, 5.3, 5.4, 5.5,
5.6, 5.7, and 5.8.''
d. Sections 5.3, 7.1, 7.2, 7.3, 7.5.6, 7.6, 7.6.1, 9.2, 10.1,
10.2.2, 10.2.5, 10.2.8, 12.3, and 12.6 are amended by revising ``ENB''
to read ``termonomer'' wherever it appears.
e. Sections 6.11, 7.5.1, 9.3.3, 11.1.2, and 12.5 are revised.
f. The first sentence in Section 7.1 is amended by revising to read
``Reagent toluene, EM Science Omnisolv (or equivalent).''
g. Section 7.2 is amended by revising the first sentence to read
``Reagent acetone, EM Science Omnisolv HR-GC (or equivalent).''
h. Section 7.3 is amended by revising the first sentence to read
``Reagent heptane, Aldrich Chemical Gold Label, Cat #15,487-3 (or
equivalent).''
i. Section 7.4.5 is amended by revising ``Section 5.4.4'' to read
``7.4.4.''
j. Section 9.3 is amended by revising the first sentence to read
``Recovery efficiency must be determined for high ethylene
concentration, low ethylene concentration, E-P terpolymer, or oil
extended samples and whenever modifications are made to the method.''
k. Section 13.1 is amended by revising the last sentence to read
``Note: These values are examples; each sample type, as specified in
Section 9.3, must be tested for sample recovery.''
The revisions read as follows:

Method 310B-Determination of Residual Hexane Through Gas
Chromatography

* * * * *

6.0 Equipment and Supplies * * *

6.11 Crimp-top sample vials and HP p/n 5181-1211 crimp caps, or
screw-top autosampler vials and screw tops.
* * * * *
7.5.1 Preparation of Polymer Dissolving Solution. Fill a 4,000-ml
volumetric flask about \3/4\ full with toluene.
* * * * *
9.3.3 The precipitated polymer from the steps described above
shall be redissolved using toluene as the solvent. No heptane shall be
added to the sample in the second dissolving step. The toluene solvent
and acetone precipitant shall be determined to be free of interfering
compounds.
* * * * *
11.1.2 Place crumb sample in bottle: RLA-3: 10 g (gives a dry wt.
of 5.5 g).
* * * * *
12.5 After obtaining the final dry weight of polymer used (Section
11.1.10 of this method), record that result in a ``dry wt.'' column of
the logbook (for oil extended polymer, the amount of oil extracted is
added to the dry rubber weight).
* * * * *

13. Appendix A to Part 63 is amended by revising Methods 303,
303A, 304A, 304B, 305, 306, 306A, and 306B to read as follows:

Method 303--Determination of Visible Emissions From By-Product Coke
Oven Batteries

Note: This method is not inclusive with respect to observer
certification. Some material is incorporated by reference from other
methods in appendix A to 40 CFR part 60. Therefore, to obtain
reliable results, persons using this method should have a thorough
knowledge of Method 9.

1.0 Scope and Application

1.1 Applicability. This method is applicable for the determination
of visible emissions (VE) from the following by-product coke oven
battery sources: charging systems during charging; doors, topside port
lids, and offtake systems on operating coke ovens; and collecting
mains. This method is also applicable for qualifying observers for
visually determining the presence of VE.

2.0 Summary of Method

2.1 A certified observer visually determines the VE from coke oven
battery sources. Certification procedures are presented. This method
does not require that opacity of emissions be determined or that
magnitude be differentiated.

3.0 Definitions

3.1 Bench means the platform structure in front of the oven doors.
3.2 By-product Coke Oven Battery means a source consisting of a
group of ovens connected by common walls, where coal undergoes
destructive distillation under positive pressure to produce coke and
coke oven gas, from which by-products are recovered.
3.3 Charge or charging period means the period of time that
commences when coal begins to flow into an oven through a topside port
and ends when the last charging port is recapped.
3.4 Charging system means an apparatus used to charge coal to a
coke oven (e.g., a larry car for wet coal charging systems).
3.5 Coke oven door means each end enclosure on the push side and
the coking side of an oven. The chuck, or leveler-bar, door is
considered part of the push side door. The coke oven door area includes
the entire area on the vertical face of a coke oven between the bench
and the top of the battery between two adjacent buck stays.
3.6 Coke side means the side of a battery from which the coke is
discharged from ovens at the end of the coking cycle.
3.7 Collecting main means any apparatus that is connected to one
or more offtake systems and that provides a passage for conveying gases
under positive pressure from the by-product coke oven battery to the
by-product recovery system.
3.8 Consecutive charges means charges observed successively,
excluding any charge during which the observer's view of the charging
system or topside ports is obscured.
3.9 Damper-off means to close off the gas passage between the coke
oven and the collecting main, with no flow of raw coke oven gas from
the collecting main into the oven or into the oven's offtake system(s).
3.10 Decarbonization period means the period of time for
combusting oven carbon that commences when the oven lids are removed
from an empty oven or when standpipe caps of an oven are opened. The
period ends with the initiation of the next charging period for that
oven.
3.11 Larry car means an apparatus used to charge coal to a coke
oven with a wet coal charging system.
3.12 Log average means logarithmic average as calculated in
Section 12.4.
3.13 Offtake system means any individual oven apparatus that is
stationary and provides a passage for gases from an oven to a coke oven
battery collecting main or to another oven. Offtake system components
include the standpipe and standpipe caps, goosenecks, stationary jumper
pipes, mini-standpipes, and standpipe and gooseneck connections.
3.14 Operating oven means any oven not out of operation for
rebuild or maintenance work extensive enough to

[[Page 62217]]

require the oven to be skipped in the charging sequence.
3.15 Oven means a chamber in the coke oven battery in which coal
undergoes destructive distillation to produce coke.
3.16 Push side means the side of the battery from which the coke
is pushed from ovens at the end of the coking cycle.
3.17 Run means the observation of visible emissions from topside
port lids, offtake systems, coke oven doors, or the charging of a
single oven in accordance with this method.
3.18 Shed means an enclosure that covers the side of the coke oven
battery, captures emissions from pushing operations and from leaking
coke oven doors on the coke side or push side of the coke oven battery,
and routes the emissions to a control device or system.
3.19 Standpipe cap means An apparatus used to cover the opening in
the gooseneck of an offtake system.
3.20 Topside port lid means a cover, removed during charging or
decarbonizing, that is placed over the opening through which coal can
be charged into the oven of a by-product coke oven battery.
3.21 Traverse time means accumulated time for a traverse as
measured by a stopwatch. Traverse time includes time to stop and write
down oven numbers but excludes time waiting for obstructions of view to
clear or for time to walk around obstacles.
3.22 Visible Emissions or VE means any emission seen by the
unaided (except for corrective lenses) eye, excluding steam or
condensing water.

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies [Reserved]

7.0 Reagents and Standards [Reserved]

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

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization

Observer certification and training requirements are as follows:
10.1 Certification Procedures. This method requires only the
determination of whether VE occur and does not require the
determination of opacity levels; therefore, observer certification
according to Method 9 in appendix A to part 60 of this chapter is not
required to obtain certification under this method. However, in order
to receive Method 303 observer certification, the first-time observer
(trainee) shall have attended the lecture portion of the Method 9
certification course. In addition, the trainee shall successfully
complete the Method 303 training course, satisfy the field observation
requirement, and demonstrate adequate performance and sufficient
knowledge of Method 303. The Method 303 training course shall be
conducted by or under the sanction of the EPA and shall consist of
classroom instruction and field observations, and a proficiency test.
10.1.1 The classroom instruction shall familiarize the trainees
with Method 303 through lecture, written training materials, and a
Method 303 demonstration video. A successful completion of the
classroom portion of the Method 303 training course shall be
demonstrated by a perfect score on a written test. If the trainee fails
to answer all of the questions correctly, the trainee may review the
appropriate portion of the training materials and retake the test.
10.1.2 The field observations shall be a minimum of 12 hours and
shall be completed before attending the Method 303 certification
course. Trainees shall observe the operation of a coke oven battery as
it pertains to Method 303, including topside operations, and shall also
practice conducting Method 303 or similar methods. During the field
observations, trainees unfamiliar with coke battery operations shall
receive instruction from an experienced coke oven observer familiar
with Method 303 or similar methods and with the operation of coke
batteries. The trainee must verify completion of at least 12 hours of
field observation prior to attending the Method 303 certification
course.
10.1.3 All trainees must demonstrate proficiency in the
application of Method 303 to a panel of three certified Method 303
observers, including an ability to differentiate coke oven emissions
from condensing water vapor and smoldering coal. Each panel member
shall have at least 120 days experience in reading visible emissions
from coke ovens. The visible emissions inspections that will satisfy
the experience requirement must be inspections of coke oven battery
fugitive emissions from the emission points subject to emission
standards under subpart L of this part (i.e., coke oven doors, topside
port lids, offtake system(s), and charging operations), using either
Method 303 or predecessor State or local test methods. A ``day's
experience'' for a particular inspection is a day on which one complete
inspection was performed for that emission point under Method 303 or a
predecessor State or local method. A ``day's experience'' does not mean
8 or 10 hours performing inspections, or any particular time expressed
in minutes or hours that may have been spent performing them. Thus, it
would be possible for an individual to qualify as a Method 303 panel
member for some emission points, but not others (e.g., an individual
might satisfy the experience requirement for coke oven doors, but not
topside port lids). Until November 15, 1994, the EPA may waive the
certification requirement (but not the experience requirement) for
panel members. The composition of the panel shall be approved by the
EPA. The panel shall observe the trainee in a series of training runs
and a series of certification runs. There shall be a minimum of 1
training run for doors, topside port lids, and offtake systems, and a
minimum of 5 training runs (i.e., 5 charges) for charging. During
training runs, the panel can advise the trainee on proper procedures.
There shall be a minimum of 3 certification runs for doors, topside
port lids, and offtake systems, and a minimum of 15 certification runs
for charging (i.e., 15 charges). The certifications runs shall be
unassisted. Following the certification test runs, the panel shall
approve or disapprove certification based on the trainee's performance
during the certification runs. To obtain certification, the trainee
shall demonstrate to the satisfaction of the panel a high degree of
proficiency in performing Method 303. To aid in evaluating the
trainee's performance, a

[[Page 62218]]

checklist, provided by the EPA, will be used by the panel members.
10.2 Observer Certification/Recertification. The coke oven
observer certification is valid for 1 year from date of issue. The
observer shall recertify annually by viewing the training video and
answering all of the questions on the certification test correctly.
Every 3 years, an observer shall be required to pass the proficiency
test in Section 10.1.3 in order to be certified.
10.3 The EPA (or applicable enforcement agency) shall maintain
records reflecting a certified observer's successful completion of the
proficiency test, which shall include the completed proficiency test
checklists for the certification runs.
10.4 An owner or operator of a coke oven battery subject to
subpart L of this part may observe a training and certification program
under this section.

11.0 Procedure

11.1 Procedure for Determining VE from Charging Systems During
Charging.
11.1.1 Number of Oven Charges. Refer to Sec. 63.309(c)(1) of this
part for the number of oven charges to observe. The observer shall
observe consecutive charges. Charges that are nonconsecutive can only
be observed when necessary to replace observations terminated prior to
the completion of a charge because of visual interferences. (See
Section 11.1.5).
11.1.2 Data Records. Record all the information requested at the
top of the charging system inspection sheet (Figure 303-1). For each
charge, record the identification number of the oven being charged, the
approximate beginning time of the charge, and the identification of the
larry car used for the charge.
11.1.3 Observer Position. Stand in an area or move to positions on
the topside of the coke oven battery with an unobstructed view of the
entire charging system. For wet coal charging systems or non-pipeline
coal charging systems, the observer should have an unobstructed view of
the emission points of the charging system, including larry car
hoppers, drop sleeves, and the topside ports of the oven being charged.
Some charging systems are configured so that all emission points can
only be seen from a distance of five ovens. For other batteries,
distances of 8 to 12 ovens are adequate.
11.1.4 Observation. The charging period begins when coal begins to
flow into the oven and ends when the last charging port is recapped.
During the charging period, observe all of the potential sources of VE
from the entire charging system. For wet coal charging systems or non-
pipeline coal charging systems, sources of VE typically include the
larry car hoppers, drop sleeves, slide gates, and topside ports on the
oven being charged. Any VE from an open standpipe cap on the oven being
charged is included as charging VE.
11.1.4.1 Using an accumulative-type stopwatch with unit divisions
of at least 0.5 seconds, determine the total time VE are observed as
follows. Upon observing any VE emerging from any part of the charging
system, start the stopwatch. Stop the watch when VE are no longer
observed emerging, and restart the watch when VE reemerges.
11.1.4.2 When VE occur simultaneously from several points during a
charge, consider the sources as one. Time overlapping VE as continuous
VE. Time single puffs of VE only for the time it takes for the puff to
emerge from the charging system. Continue to time VE in this manner for
the entire charging period. Record the accumulated time to the nearest
0.5 second under ``Visible emissions, seconds'' on Figure 303-1.
11.1.5 Visual Interference. If fugitive VE from other sources at
the coke oven battery site (e.g., door leaks or condensing water vapor
from the coke oven wharf) prevent a clear view of the charging system
during a charge, stop the stopwatch and make an appropriate notation
under ``Comments'' on Figure 303-1. Label the observation an
observation of an incomplete charge, and observe another charge to
fulfill the requirements of Section 11.1.1.
11.1.6 VE Exemptions. Do not time the following VE:
11.1.6.1 The VE from burning or smoldering coal spilled on top of
the oven, topside port lid, or larry car surfaces;

Note: The VE from smoldering coal are generally white or gray.
These VE generally have a plume of less than 1 meter long. If the
observer cannot safely and with reasonable confidence determine that
VE are from charging, do not count them as charging emissions.

11.1.6.2 The VE from the coke oven doors or from the leveler bar;
or
11.1.6.3 The VE that drift from the top of a larry car hopper if
the emissions had already been timed as VE from the drop sleeve.

Note: When the slide gate on a larry car hopper closes after the
coal has been added to the oven, the seal may not be airtight. On
occasions, a puff of smoke observed at the drop sleeves is forced
past the slide gate up into the larry car hopper and may drift from
the top; time these VE either at the drop sleeves or the hopper. If
the larry car hopper does not have a slide gate or the slide gate is
left open or partially closed, VE may quickly pass through the larry
car hopper without being observed at the drop sleeves and will
appear as a strong surge of smoke; time these as charging VE.

11.1.7 Total Time Record. Record the total time that VE were
observed for each charging operation in the appropriate column on the
charging system inspection sheet.
11.1.8 Determination of Validity of a Set of Observations. Five
charging observations (runs) obtained in accordance with this method
shall be considered a valid set of observations for that day. No
observation of an incomplete charge shall be included in a daily set of
observations that is lower than the lowest reading for a complete
charge. If both complete and incomplete charges have been observed, the
daily set of observations shall include the five highest values
observed. Four or three charging observations (runs) obtained in
accordance with this method shall be considered a valid set of charging
observations only where it is not possible to obtain five charging
observations, because visual interferences (see Section 11.1.5) or
inclement weather prevent a clear view of the charging system during
charging. However, observations from three or four charges that satisfy
these requirements shall not be considered a valid set of charging
observations if use of such set of observations in a calculation under
Section 12.4 would cause the value of A to be less than 145.
11.1.9 Log Average. For each day on which a valid daily set of
observations is obtained, calculate the daily 30-day rolling log
average of seconds of visible emissions from the charging operation for
each battery using these data and the 29 previous valid daily sets of
observations, in accordance with Section 12.4.
11.2. Procedure for Determining VE from Coke Oven Door Areas. The
intent of this procedure is to determine VE from coke oven door areas
by carefully observing the door area from a standard distance while
walking at a normal pace.
11.2.1 Number of Runs. Refer to Sec. 63.309(c)(1) of this part for
the appropriate number of runs.
11.2.2 Battery Traverse. To conduct a battery traverse, walk the
length of the battery on the outside of the pusher machine and quench
car tracks at a steady, normal walking pace, pausing to make
appropriate entries on the door area inspection sheet (Figure 303-2). A
single test run consists of two timed traverses, one for the coke side
and one for the push side. The walking pace shall be such that the
duration of the traverse does not exceed an average of

[[Page 62219]]

4 seconds per oven door, excluding time spent moving around stationary
obstructions or waiting for other obstructions to move from positions
blocking the view of a series of doors. Extra time is allowed for each
leak (a maximum of 10 additional seconds for each leaking door) for the
observer to make the proper notation. A walking pace of 3 seconds per
oven door has been found to be typical. Record the actual traverse time
with a stopwatch.
11.2.2.1 Include in the traverse time only the time spent
observing the doors and recording door leaks. To measure actual
traverse time, use an accumulative-type stopwatch with unit divisions
of 0.5 seconds or less. Exclude interruptions to the traverse and time
required for the observer to move to positions where the view of the
battery is unobstructed, or for obstructions, such as the door machine,
to move from positions blocking the view of a series of doors.
11.2.2.2 Various situations may arise that will prevent the
observer from viewing a door or a series of doors. Prior to the door
inspection, the owner or operator may elect to temporarily suspend
charging operations for the duration of the inspection, so that all of
the doors can be viewed by the observer. The observer has two options
for dealing with obstructions to view: (a) Stop the stopwatch and wait
for the equipment to move or the fugitive emissions to dissipate before
completing the traverse; or (b) stop the stopwatch, skip the affected
ovens, and move to an unobstructed position to continue the traverse.
Restart the stopwatch and continue the traverse. After the completion
of the traverse, if the equipment has moved or the fugitive emissions
have dissipated, inspect the affected doors. If the equipment is still
preventing the observer from viewing the doors, then the affected doors
may be counted as not observed. If option (b) is used because of doors
blocked by machines during charging operations, then, of the affected
doors, exclude the door from the most recently charged oven from the
inspection. Record the oven numbers and make an appropriate notation
under ``Comments'' on the door area inspection sheet (Figure 303-2).
11.2.2.3 When batteries have sheds to control emissions, conduct
the inspection from outside the shed unless the doors cannot be
adequately viewed. In this case, conduct the inspection from the bench.
Be aware of special safety considerations pertinent to walking on the
bench and follow the instructions of company personnel on the required
equipment and procedures. If possible, conduct the bench traverse
whenever the bench is clear of the door machine and hot coke guide.
11.2.3 Observations. Record all the information requested at the
top of the door area inspection sheet (Figure 303-2), including the
number of non-operating ovens. Record the clock time at the start of
the traverse on each side of the battery. Record which side is being
inspected (i.e., coke side or push side). Other information may be
recorded at the discretion of the observer, such as the location of the
leak (e.g., top of the door, chuck door, etc.), the reason for any
interruption of the traverse, or the position of the sun relative to
the battery and sky conditions (e.g., overcast, partly sunny, etc.).
11.2.3.1 Begin the test run by starting the stopwatch and
traversing either the coke side or the push side of the battery. After
completing one side, stop the watch. Complete this procedure on the
other side. If inspecting more than one battery, the observer may view
the push sides and the coke sides sequentially.
11.2.3.2 During the traverse, look around the entire perimeter of
each oven door. The door is considered leaking if VE are detected in
the coke oven door area. The coke oven door area includes the entire
area on the vertical face of a coke oven between the bench and the top
of the battery between two adjacent buck stays (e.g., the oven door,
chuck door, between the masonry brick, buck stay or jamb, or other
sources). Record the oven number and make the appropriate notation on
the door area inspection sheet (Figure 303-2).

Note: Multiple VE from the same door area (e.g., VE from both
the chuck door and the push side door) are counted as only one
emitting door, not as multiple emitting doors.

11.2.3.3 Do not record the following sources as door area VE:
11.2.3.3.1 VE from ovens with doors removed. Record the oven
number and make an appropriate notation under ``Comments;''
11.2.3.3.2 VE from ovens taken out of service. The owner or
operator shall notify the observer as to which ovens are out of
service. Record the oven number and make an appropriate notation under
``Comments;'' or
11.2.3.3.3 VE from hot coke that has been spilled on the bench as
a result of pushing.
11.2.4 Criteria for Acceptance. After completing the run,
calculate the maximum time allowed to observe the ovens using the
equation in Section 12.2. If the total traverse time exceeds T, void
the run, and conduct another run to satisfy the requirements of
Sec. 63.309(c)(1) of this part.
11.2.5 Percent Leaking Doors. For each day on which a valid
observation is obtained, calculate the daily 30-day rolling average for
each battery using these data and the 29 previous valid daily
observations, in accordance with Section 12.5.
11.3 Procedure for Determining VE from Topside Port Lids and
Offtake Systems.
11.3.1 Number of Runs. Refer to Sec. 63.309(c)(1) of this part for
the number of runs to be conducted. Simultaneous runs or separate runs
for the topside port lids and offtake systems may be conducted.
11.3.2 Battery Traverse. To conduct a topside traverse of the
battery, walk the length of the battery at a steady, normal walking
pace, pausing only to make appropriate entries on the topside
inspection sheet (Figure 303-3). The walking pace shall not exceed an
average rate of 4 seconds per oven, excluding time spent moving around
stationary obstructions or waiting for other obstructions to move from
positions blocking the view. Extra time is allowed for each leak for
the observer to make the proper notation. A walking pace of 3 seconds
per oven is typical. Record the actual traverse time with a stopwatch.
11.3.3 Topside Port Lid Observations. To observe lids of the ovens
involved in the charging operation, the observer shall wait to view the
lids until approximately 5 minutes after the completion of the charge.
Record all the information requested on the topside inspection sheet
(Figure 303-3). Record the clock time when traverses begin and end. If
the observer's view is obstructed during the traverse (e.g., steam from
the coke wharf, larry car, etc.), follow the guidelines given in
Section 11.2.2.2.
11.3.3.1 To perform a test run, conduct a single traverse on the
topside of the battery. The observer shall walk near the center of the
battery but may deviate from this path to avoid safety hazards (such as
open or closed charging ports, luting buckets, lid removal bars, and
topside port lids that have been removed) and any other obstacles. Upon
noting VE from the topside port lid(s) of an oven, record the oven
number and port number, then resume the traverse. If any oven is
dampered-off from the collecting main for decarbonization, note this
under ``Comments'' for that particular oven.

Note: Count the number of topside ports, not the number of
points, exhibiting VE, i.e., if a topside port has several points of
VE, count this as one port exhibiting VE.

[[Page 62220]]

11.3.3.2 Do not count the following as topside port lid VE:
11.3.3.2.1 VE from between the brickwork and oven lid casing or VE
from cracks in the oven brickwork. Note these VE under ``Comments;''
11.3.3.2.2 VE from topside ports involved in a charging operation.
Record the oven number, and make an appropriate notation (e.g., not
observed because ports open for charging) under ``Comments;''
11.3.3.2.3 Topside ports having maintenance work done. Record the
oven number and make an appropriate notation under ``Comments;'' or
11.3.3.2.4 Condensing water from wet-sealing material. Ports with
only visible condensing water from wet-sealing material are counted as
observed but not as having VE.
11.3.3.2.5 Visible emissions from the flue inspection ports and
caps.
11.3.4 Offtake Systems Observations. To perform a test run,
traverse the battery as in Section 11.3.3.1. Look ahead and back two to
four ovens to get a clear view of the entire offtake system for each
oven. Consider visible emissions from the following points as offtake
system VE: (a) the flange between the gooseneck and collecting main
(``saddle''), (b) the junction point of the standpipe and oven
(``standpipe base''), (c) the other parts of the offtake system (e.g.,
the standpipe cap), and (d) the junction points with ovens and flanges
of jumper pipes.
11.3.4.1 Do not stray from the traverse line in order to get a
``closer look'' at any part of the offtake system unless it is to
distinguish leaks from interferences from other sources or to avoid
obstacles.
11.3.4.2 If the centerline does not provide a clear view of the
entire offtake system for each oven (e.g., when standpipes are longer
than 15 feet), the observer may conduct the traverse farther from
(rather than closer to) the offtake systems.
11.3.4.3 Upon noting a leak from an offtake system during a
traverse, record the oven number. Resume the traverse. If the oven is
dampered-off from the collecting main for decarbonization and VE are
observed, note this under ``Comments'' for that particular oven.
11.3.4.4 If any part or parts of an offtake system have VE, count
it as one emitting offtake system. Each stationary jumper pipe is
considered a single offtake system.
11.3.4.5 Do not count standpipe caps open for a decarbonization
period or standpipes of an oven being charged as source of offtake
system VE. Record the oven number and write ``Not observed'' and the
reason (i.e., decarb or charging) under ``Comments.''

Note: VE from open standpipes of an oven being charged count as
charging emissions. All VE from closed standpipe caps count as
offtake leaks.

11.3.5 Criteria for Acceptance. After completing the run (allow 2
traverses for batteries with double mains), calculate the maximum time
allowed to observe the topside port lids and/or offtake systems using
the equation in Section 12.3. If the total traverse time exceeds T,
void the run and conduct another run to satisfy the requirements of
Sec. 63.309(c)(1) of this part.
11.3.6 In determining the percent leaking topside port lids and
percent leaking offtake systems, do not include topside port lids or
offtake systems with VE from the following ovens:
11.3.6.1 Empty ovens, including ovens undergoing maintenance,
which are properly dampered off from the main.
11.3.6.2 Ovens being charged or being pushed.
11.3.6.3 Up to 3 full ovens that have been dampered off from the
main prior to pushing.
11.3.6.4 Up to 3 additional full ovens in the pushing sequence
that have been dampered off from the main for offtake system cleaning,
for decarbonization, for safety reasons, or when a charging/pushing
schedule involves widely separated ovens (e.g., a Marquard system); or
that have been dampered off from the main for maintenance near the end
of the coking cycle. Examples of reasons that ovens are dampered off
for safety reasons are to avoid exposing workers in areas with
insufficient clearance between standpipes and the larry car, or in
areas where workers could be exposed to flames or hot gases from open
standpipes, and to avoid the potential for removing a door on an oven
that is not dampered off from the main.
11.3.7 Percent Leaking Topside Port Lids and Offtake Systems. For
each day on which a valid observation is obtained, calculate the daily
30-day rolling average for each battery using these data and the 29
previous valid daily observations, in accordance with Sections 12.6 and
12.7.
11.4 Procedure for Determining VE from Collecting Mains.
11.4.1 Traverse. To perform a test run, traverse both the
collecting main catwalk and the battery topside along the side closest
to the collecting main. If the battery has a double main, conduct two
sets of traverses for each run, i.e., one set for each main.
11.4.2 Data Recording. Upon noting VE from any portion of a
collection main, identify the source and approximate location of the
source of VE and record the time under ``Collecting main'' on Figure
303-3; then resume the traverse.
11.4.3 Collecting Main Pressure Check. After the completion of the
door traverse, the topside port lids, and offtake systems, compare the
collecting main pressure during the inspection to the collecting main
pressure during the previous 8 to 24 hours. Record the following: (a)
the pressure during inspection, (b) presence of pressure deviation from
normal operations, and (c) the explanation for any pressure deviation
from normal operations, if any, offered by the operators. The owner or
operator of the coke battery shall maintain the pressure recording
equipment and conduct the quality assurance/quality control (QA/QC)
necessary to ensure reliable pressure readings and shall keep the QA/QC
records for at least 6 months. The observer may periodically check the
QA/QC records to determine their completeness. The owner or operator
shall provide access to the records within 1 hour of an observer's
request.

12.0 Data Analysis and Calculations

12.1 Nomenclature.

A = 150 or the number of valid observations (runs). The value of A
shall not be less than 145, except for purposes of determinations under
Sec. 63.306(c) (work practice plan implementation) or Sec. 63.306(d)
(work practice plan revisions) of this part. No set of observations
shall be considered valid for such a recalculation that otherwise would
not be considered a valid set of observations for a calculation under
this paragraph.
Di = Number of doors on non-operating ovens.
Dno = Number of doors not observed.
Dob = Total number of doors observed on operating ovens.
Dt = Total number of oven doors on the battery.
e = 2.72
J = Number of stationary jumper pipes.
L = Number of doors with VE.
Lb = Yard-equivalent reading.
Ls = Number of doors with VE observed from the bench under
sheds.
Ly = Number of doors with VE observed from the yard.
Ly = Number of doors with VE observed from the yard on the
push side.
ln = Natural logarithm.
N = Total number of ovens in the battery.
Ni = Total number of inoperable ovens.
PNO = Number of ports not observed.
Povn = Number of ports per oven.

[[Page 62221]]

PVE = Number of topside port lids with VE.
PLD = Percent leaking coke oven doors for the test run.
PLL = Percent leaking topside port lids for the run.
PLO = Percent leaking offtake systems.
T = Total time allowed for traverse, seconds.
Tovn = Number of offtake systems (excluding jumper pipes)
per oven.
TNO = Number of offtake systems not observed.
TVE = Number of offtake systems with VE.
Xi = Seconds of VE during the ith charge.
Z = Number of topside port lids or offtake systems with VE.

12.2 Criteria for Acceptance for VE Determinations from Coke Oven
Door Areas. After completing the run, calculate the maximum time
allowed to observe the ovens using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.535

12.3 Criteria for Acceptance for VE Determinations from Topside
Port Lids and Offtake Systems. After completing the run (allow 2
traverses for batteries with double mains), calculate the maximum time
allowed to observe the topside port lids and/or offtake systems by the
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.536

12.4 Average Duration of VE from Charging Operations. Use Equation
303-3 to calculate the daily 30-day rolling log average of seconds of
visible emissions from the charging operation for each battery using
these current day's observations and the 29 previous valid daily sets
of observations.
[GRAPHIC] [TIFF OMITTED] TR17OC00.537

12.5 Percent Leaking Doors (PLD). Determine the total number of
doors for which observations were made on the coke oven battery as
follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.538

12.5.1 For each test run (one run includes both the coke side and
the push side traverses), sum the number of doors with door area VE.
For batteries subject to an approved alternative standard under
Sec. 63.305 of this part, calculate the push side and the coke side PLD
separately.
12.5.2 Calculate percent leaking doors by using Equation 303-5:
[GRAPHIC] [TIFF OMITTED] TR17OC00.539

12.5.3 When traverses are conducted from the bench under sheds,
calculate the coke side and the push side separately. Use Equation 303-
6 to calculate a yard-equivalent reading:
[GRAPHIC] [TIFF OMITTED] TR17OC00.540

If Lb is less than zero, use zero for Lb in
Equation 303-7 in the calculation of PLD.
12.5.3.1 Use Equation 303-7 to calculate PLD:
[GRAPHIC] [TIFF OMITTED] TR17OC00.541

Round off PLD to the nearest hundredth of 1 percent and record as the
percent leaking coke oven doors for the run.
12.5.3.2 Average Percent Leaking Doors. Use Equation 303-8 to
calculate the daily 30-day rolling average percent leaking doors for
each battery using these current day's observations and the 29 previous
valid daily sets of observations.
[GRAPHIC] [TIFF OMITTED] TR17OC00.542

12.6 Topside Port Lids. Determine the percent leaking topside port
lids for each run as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.543

12.6.1 Round off this percentage to the nearest hundredth of 1
percent and record this percentage as the percent leaking topside port
lids for the run.
12.6.2 Average Percent Leaking Topside Port Lids. Use Equation
303-10 to calculate the daily 30-day rolling average percent leaking
topside port lids for each battery using these current day's
observations and the 29 previous valid daily sets of observations.

[[Page 62222]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.544

12.7 Offtake Systems. Determine the percent leaking offtake
systems for the run as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.545

12.7.1 Round off this percentage to the nearest hundredth of 1
percent and record this percentage as the percent leaking offtake
systems for the run.
12.7.2 Average Percent Leaking Offtake Systems. Use Equation 303-
12 to calculate the daily 30-day rolling average percent leaking
offtake systems for each battery using these current day's observations
and the 29 previous valid daily sets of observations.
[GRAPHIC] [TIFF OMITTED] TR17OC00.546

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References.

1. Missan, R., and A. Stein. Guidelines for Evaluation of
Visible Emissions Certification, Field Procedures, Legal Aspects,
and Background Material. U.S. Environmental Protection Agency. EPA
Publication No. EPA-340/1-75-007. April 1975.
2. Wohlschlegel, P., and D. E. Wagoner. Guideline for
Development of a Quality Assurance Program: Volume IX--Visual
Determination of Opacity Emission from Stationary Sources. U.S.
Environmental Protection Agency. EPA Publication No. EPA-650/4-74-
005i. November 1975.
3. U.S. Occupational Safety and Health Administration. Code of
Federal Regulations. Title 29, Chapter XVII, Section 1910.1029(g).
Washington, D.C. Government Printing Office. July 1, 1990.
4. U.S. Environmental Protection Agency. National Emission
Standards for Hazardous Air Pollutants; Coke Oven Emissions from
Wet-Coal Charged By-Product Coke Oven Batteries; Proposed Rule and
Notice of Public Hearing. Washington, D.C. Federal Register. Vol.
52, No. 78 (13586). April 23, 1987.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

Company name:----------------------------------------------------------
Battery no.: ______ Date: ______ Run no.: ______
City, State:-----------------------------------------------------------
Observer name:---------------------------------------------------------
Company representative(s):---------------------------------------------

----------------------------------------------------------------------------------------------------------------
Visible emissions,
Charge No. Oven No. Clock time seconds Comments
----------------------------------------------------------------------------------------------------------------

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

[[Page 62223]]

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

Figure 303-1. Charging System Inspection
Company name:---------------------------------------------------------
Battery no.:----------------------------------------------------------
Date:-----------------------------------------------------------------
City, State:----------------------------------------------------------
Total no. of ovens in battery:----------------------------------------
Observer name:--------------------------------------------------------
Certification expiration date:----------------------------------------
Inoperable ovens:-----------------------------------------------------
Company representative(s):--------------------------------------------
Traverse time CS:-----------------------------------------------------
Traverse time PS:-----------------------------------------------------
Valid run (Y or N):---------------------------------------------------

----------------------------------------------------------------------------------------------------------------
Comments (No. of blocked doors,
Time traverse started/completed PS/CS Door No. interruptions to traverse, etc.)
----------------------------------------------------------------------------------------------------------------

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

Figure 303-2. Door Area Inspection.

[[Page 62224]]

Company name:---------------------------------------------------------
Battery no.:----------------------------------------------------------
Date:-----------------------------------------------------------------
City, State:----------------------------------------------------------
Total no. of ovens in battery:----------------------------------------
Observer name:--------------------------------------------------------
Certification expiration date:----------------------------------------
Inoperable ovens:-----------------------------------------------------
Company representative(s):--------------------------------------------
Total no. of lids:----------------------------------------------------
Total no. of offtakes:------------------------------------------------
Total no. of jumper pipes:--------------------------------------------
Ovens not observed:---------------------------------------------------
Total traverse time:--------------------------------------------------
Valid run (Y or N):---------------------------------------------------

----------------------------------------------------------------------------------------------------------------
Type of Inspection
Time traverse started/completed (lids, offtakes, Location of VE (Oven #/Port #) Comments
collecting main)
----------------------------------------------------------------------------------------------------------------

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

Figure 303-3. Topside Inspection

Method 303A--Determination of Visible Emissions From Nonrecovery
Coke Oven Batteries

Note: This method does not include all of the specifications
pertaining to observer certification. 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 Method 9 and Method
303.

1.0 Scope and Application

1.1 Applicability. This method is applicable for the determination
of visible emissions (VE) from leaking doors at nonrecovery coke oven
batteries.

2.0 Summary of Method

2.1 A certified observer visually determines the VE from coke oven
battery sources while walking at a normal pace. This method does not
require that opacity of emissions be determined or that magnitude be
differentiated.

3.0 Definitions

3.1 Bench means the platform structure in front of the oven doors.

[[Page 62225]]

3.2 Coke oven door means each end enclosure on the push side and
the coking side of an oven.
3.3 Coke side means the side of a battery from which the coke is
discharged from ovens at the end of the coking cycle.
3.4 Nonrecovery coke oven battery means a source consisting of a
group of ovens connected by common walls and operated as a unit, where
coal undergoes destructive distillation under negative pressure to
produce coke, and which is designed for the combustion of coke oven gas
from which by-products are not recovered.
3.5 Operating oven means any oven not out of operation for rebuild
or maintenance work extensive enough to require the oven to be skipped
in the charging sequence.
3.6 Oven means a chamber in the coke oven battery in which coal
undergoes destructive distillation to produce coke.
3.7 Push side means the side of the battery from which the coke is
pushed from ovens at the end of the coking cycle.
3.8 Run means the observation of visible emissions from coke oven
doors in accordance with this method.
3.9 Shed means an enclosure that covers the side of the coke oven
battery, captures emissions from pushing operations and from leaking
coke oven doors on the coke side or push side of the coke oven battery,
and routes the emissions to a control device or system.
3.10 Traverse time means accumulated time for a traverse as
measured by a stopwatch. Traverse time includes time to stop and write
down oven numbers but excludes time waiting for obstructions of view to
clear or for time to walk around obstacles.
3.11 Visible Emissions or VE means any emission seen by the
unaided (except for corrective lenses) eye, excluding steam or
condensing water.

4.0 Interferences. [Reserved]

5.0 Safety

6.0 Equipment and Supplies. [Reserved]

7.0 Reagents and Standards [Reserved]

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

9.0 Quality Control. [Reserved]

10.0 Calibration and Standardization.

10.1 Training. This method requires only the determination of
whether VE occur and does not require the determination of opacity
levels; therefore, observer certification according to Method 9 in
Appendix A to Part 60 is not required. However, the first-time observer
(trainee) shall have attended the lecture portion of the Method 9
certification course. Furthermore, before conducting any VE
observations, an observer shall become familiar with nonrecovery coke
oven battery operations and with this test method by observing for a
minimum of 4 hours the operation of a nonrecovery coke oven battery in
the presence of personnel experienced in performing Method 303
assessments.

11.0 Procedure

The intent of this procedure is to determine VE from coke oven door
areas by carefully observing the door area while walking at a normal
pace.
11.1 Number of Runs. Refer to Sec. 63.309(c)(1) of this part for
the appropriate number of runs.
11.2 Battery Traverse. To conduct a battery traverse, walk the
length of the battery on the outside of the pusher machine and quench
car tracks at a steady, normal walking pace, pausing to make
appropriate entries on the door area inspection sheet (Figure 303A-1).
The walking pace shall be such that the duration of the traverse does
not exceed an average of 4 seconds per oven door, excluding time spent
moving around stationary obstructions or waiting for other obstructions
to move from positions blocking the view of a series of doors. Extra
time is allowed for each leak (a maximum of 10 additional seconds for
each leaking door) for the observer to make the proper notation. A
walking pace of 3 seconds per oven door has been found to be typical.
Record the actual traverse time with a stopwatch. A single test run
consists of two timed traverses, one for the coke side and one for the
push side.
11.2.1 Various situations may arise that will prevent the observer
from viewing a door or a series of doors. The observer has two options
for dealing with obstructions to view: (a) Wait for the equipment to
move or the fugitive emissions to dissipate before completing the
traverse; or (b) skip the affected ovens and move to an unobstructed
position to continue the traverse. Continue the traverse. After the
completion of the traverse, if the equipment has moved or the fugitive
emissions have dissipated, complete the traverse by inspecting the
affected doors. Record the oven numbers and make an appropriate
notation under ``Comments'' on the door area inspection sheet (Figure
303A-1).

Note: Extra time incurred for handling obstructions is not
counted in the traverse time.

11.2.2 When batteries have sheds to control pushing emissions,
conduct the inspection from outside the shed, if the shed allows such
observations, or from the bench. Be aware of special safety
considerations pertinent to walking on the bench and follow the
instructions of company personnel on the required equipment and
operations procedures. If possible, conduct the bench traverse whenever
the bench is clear of the door machine and hot coke guide.
11.3 Observations. Record all the information requested at the top
of the door area inspection sheet (Figure 303A-1), including the number
of non-operating ovens. Record which side is being inspected, i.e.,
coke side or push side. Other information may be recorded at the
discretion of the observer, such as the location of the leak (e.g., top
of the door), the reason for any interruption of the traverse, or the
position of the sun relative to the battery and sky conditions (e.g.,
overcast, partly sunny, etc.).
11.3.1 Begin the test run by traversing either the coke side or
the push side of the battery. After completing one side, traverse the
other side.
11.3.2 During the traverse, look around the entire perimeter of
each oven door. The door is considered leaking if VE are detected in
the coke oven door area. The coke oven door area includes the entire
area on the vertical face of a coke oven between the bench and the top
of the battery and the

[[Page 62226]]

adjacent doors on both sides. Record the oven number and make the
appropriate notation on the door area inspection sheet (Figure 303A-1).
11.3.3 Do not record the following sources as door area VE:
11.3.3.1 VE from ovens with doors removed. Record the oven number
and make an appropriate notation under ``Comments'';
11.3.3.2 VE from ovens where maintenance work is being conducted.
Record the oven number and make an appropriate notation under
``Comments''; or
11.3.3.3 VE from hot coke that has been spilled on the bench as a
result of pushing.

12.0 Data Analysis and Calculations

Same as Method 303, Section 12.1, 12.2, 12.3, 12.4, and 12.5.

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

Same as Method 303, Section 16.0.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

Company name:---------------------------------------------------------
Battery no.:----------------------------------------------------------
Date:-----------------------------------------------------------------
City, State:----------------------------------------------------------
Total no. of ovens in battery:----------------------------------------
Observer name:--------------------------------------------------------
Certification expiration date:----------------------------------------
Inoperable ovens:-----------------------------------------------------
Company representative(s):--------------------------------------------
Traverse time CS:-----------------------------------------------------
Traverse time PS:-----------------------------------------------------
Valid run (Y or N):---------------------------------------------------

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

Figure 303A-1. Door Area Inspection

[[Page 62227]]

Method 304A: Determination of Biodegradation Rates of Organic
Compounds (Vent Option)

1.0 Scope and Application

1.1 Applicability. This method is applicable for the determination
of biodegradation rates of organic compounds in an activated sludge
process. The test method is designed to evaluate the ability of an
aerobic biological reaction system to degrade or destroy specific
components in waste streams. The method may also be used to determine
the effects of changes in wastewater composition on operation. The
biodegradation rates determined by utilizing this method are not
representative of a full-scale system. The rates measured by this
method shall be used in conjunction with the procedures listed in
appendix C of this part to calculate the fraction emitted to the air
versus the fraction biodegraded.

2.0 Summary of Method

2.1 A self-contained benchtop bioreactor system is assembled in
the laboratory. A sample of mixed liquor is added and the waste stream
is then fed continuously. The benchtop bioreactor is operated under
conditions nearly identical to the target full-scale activated sludge
process. Bioreactor temperature, dissolved oxygen concentration,
average residence time in the reactor, waste composition, biomass
concentration, and biomass composition of the full-scale process are
the parameters which are duplicated in the benchtop bioreactor. Biomass
shall be removed from the target full-scale activated sludge unit and
held for no more than 4 hours prior to use in the benchtop bioreactor.
If antifoaming agents are used in the full-scale system, they shall
also be used in the benchtop bioreactor. The feed flowing into and the
effluent exiting the benchtop bioreactor are analyzed to determine the
biodegradation rates of the target compounds. The flow rate of the exit
vent is used to calculate the concentration of target compounds
(utilizing Henry's law) in the exit gas stream. If Henry's law
constants for the compounds of interest are not known, this method
cannot be used in the determination of the biodegradation rate and
Method 304B is the suggested method. The choice of analytical
methodology for measuring the compounds of interest at the inlet and
outlet to the benchtop bioreactor are left to the discretion of the
source, except where validated methods are available.

3.0 Definitions. [Reserved]

4.0 Interferences. [Reserved]

5.0 Safety

5.1 If explosive gases are produced as a byproduct of
biodegradation and could realistically pose a hazard, closely monitor
headspace concentration of these gases to ensure laboratory safety.
Placement of the benchtop bioreactor system inside a laboratory hood is
recommended regardless of byproducts produced.

6.0. Equipment and Supplies

Note: Figure 304A-1 illustrates a typical laboratory apparatus
used to measure biodegradation rates. While the following
description refers to Figure 304A-1, the EPA recognizes that
alternative reactor configurations, such as alternative reactor
shapes and locations of probes and the feed inlet, will also meet
the intent of this method. Ensure that the benchtop bioreactor
system is self-contained and isolated from the atmosphere (except
for the exit vent stream) by leak-checking fittings, tubing, etc.

6.1 Benchtop Bioreactor. The biological reaction is conducted in a
biological oxidation reactor of at least 6 liters capacity. The
benchtop bioreactor is sealed and equipped with internal probes for
controlling and monitoring dissolved oxygen and internal temperature.
The top of the reactor is equipped for aerators, gas flow ports, and
instrumentation (while ensuring that no leaks to the atmosphere exist
around the fittings).
6.2 Aeration gas. Aeration gas is added to the benchtop bioreactor
through three diffusers, which are glass tubes that extend to the
bottom fifth of the reactor depth. A pure oxygen pressurized cylinder
is recommended in order to maintain the specified oxygen concentration.
Install a blower (e.g., Diaphragm Type, 15 SCFH capacity) to blow the
aeration gas into the reactor diffusers. Measure the aeration gas flow
rate with a rotameter (e.g., 0-15 SCFH recommended). The aeration gas
will rise through the benchtop bioreactor, dissolving oxygen into the
mixture in the process. The aeration gas must provide sufficient
agitation to keep the solids in suspension. Provide an exit for the
aeration gas from the top flange of the benchtop bioreactor through a
water-cooled (e.g., Allihn-type) vertical condenser. Install the
condenser through a gas-tight fitting in the benchtop bioreactor
closure. Install a splitter which directs a portion of the gas to an
exit vent and the rest of the gas through an air recycle pump back to
the benchtop bioreactor. Monitor and record the flow rate through the
exit vent at least 3 times per day throughout the day.
6.3 Wastewater Feed. Supply the wastewater feed to the benchtop
bioreactor in a collapsible low-density polyethylene container or
collapsible liner in a container (e.g., 20 L) equipped with a spigot
cap (collapsible containers or liners of other material may be required
due to the permeability of some volatile compounds through
polyethylene). Obtain the wastewater feed by sampling the wastewater
feed in the target process. A representative sample of wastewater shall
be obtained from the piping leading to the aeration tank. This sample
may be obtained from existing sampling valves at the discharge of the
wastewater feed pump, or collected from a pipe discharging to the
aeration tank, or by pumping from a well-mixed equalization tank
upstream from the aeration tank. Alternatively, wastewater can be
pumped continuously to the laboratory apparatus from a bleed stream
taken from the equalization tank of the full-scale treatment system.
6.3.1 Refrigeration System. Keep the wastewater feed cool by ice
or by refrigeration to 4 deg.C. If using a bleed stream from the
equalization tank, refrigeration is not required if the residence time
in the bleed stream is less than five minutes.
6.3.2 Wastewater Feed Pump. The wastewater is pumped from the
refrigerated container using a variable-speed peristaltic pump drive
equipped with a peristaltic pump head. Add the feed solution to the
benchtop bioreactor through a fitting on the top flange. Determine the
rate of feed addition to provide a retention time in the benchtop
bioreactor that is numerically equivalent to the retention time in the
full-scale system. The wastewater shall be fed at a rate sufficient to
achieve 90 to 100 percent of the full-scale system residence time.
6.3.3 Treated wastewater feed. The benchtop bioreactor effluent
exits at the bottom of the reactor through a tube and proceeds to the
clarifier.
6.4 Clarifier. The effluent flows to a separate closed clarifier
that allows separation of biomass and effluent (e.g., 2-liter pear-
shaped glass separatory funnel, modified by removing the stopcock and
adding a 25-mm OD glass tube at the bottom). Benchtop bioreactor
effluent enters the clarifier through a tube inserted to a depth of
0.08 m (3 in.) through a stopper at the top of the

[[Page 62228]]

clarifier. System effluent flows from a tube inserted through the
stopper at the top of the clarifier to a drain (or sample bottle when
sampling). The underflow from the clarifier leaves from the glass tube
at the bottom of the clarifier. Flexible tubing connects this fitting
to the sludge recycle pump. This pump is coupled to a variable speed
pump drive. The discharge from this pump is returned through a tube
inserted in a port on the side of the benchtop bioreactor. An
additional port is provided near the bottom of the benchtop bioreactor
for sampling the reactor contents. The mixed liquor from the benchtop
bioreactor flows into the center of the clarifier. The clarified system
effluent separates from the biomass and flows through an exit near the
top of the clarifier. There shall be no headspace in the clarifier.
6.5 Temperature Control Apparatus. Capable of maintaining the
system at a temperature equal to the temperature of the full-scale
system. The average temperature should be maintained within
2 deg.C of the set point.
6.5.1 Temperature Monitoring Device. A resistance type temperature
probe or a thermocouple connected to a temperature readout with a
resolution of 0.1 deg.C or better.
6.5.2 Benchtop Bioreactor Heater. The heater is connected to the
temperature control device.
6.6 Oxygen Control System. Maintain the dissolved oxygen
concentration at the levels present in the full-scale system. Target
full-scale activated sludge systems with dissolved oxygen concentration
below 2 mg/L are required to maintain the dissolved oxygen
concentration in the benchtop ioreactor within 0.5 mg/L of the target
dissolved oxygen level. Target full-scale activated sludge systems with
dissolved oxygen concentration above 2 mg/L are required to maintain
the dissolved oxygen concentration in the benchtop bioreactor within
1.5 mg/L of the target dissolved oxygen concentration; however, for
target full-scale activated sludge systems with dissolved oxygen
concentrations above 2 mg/L, the dissolved oxygen concentration in the
benchtop bioreactor may not drop below 1.5 mg/L. If the benchtop
bioreactor is outside the control range, the dissolved oxygen is noted
and the reactor operation is adjusted.
6.6.1 Dissolved Oxygen Monitor. Dissolved oxygen is monitored with
a polarographic probe (gas permeable membrane) connected to a dissolved
oxygen meter (e.g., 0 to 15 mg/L, 0 to 50 deg.C).
6.6.2 Benchtop Bioreactor Pressure Monitor. The benchtop
bioreactor pressure is monitored through a port in the top flange of
the reactor. This is connected to a gauge control with a span of 13-cm
water vacuum to 13-cm water pressure or better. A relay is activated
when the vacuum exceeds an adjustable setpoint which opens a solenoid
valve (normally closed), admitting oxygen to the system. The vacuum
setpoint controlling oxygen addition to the system shall be set at
approximately 2.5 0.5 cm water and maintained at this
setting except during brief periods when the dissolved oxygen
concentration is adjusted.
6.7 Connecting Tubing. All connecting tubing shall be Teflon or
equivalent in impermeability. The only exception to this specification
is the tubing directly inside the pump head of the wastewater feed
pump, which may be Viton, Silicone or another type of flexible tubing.

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

7.0 Reagents and Standards

7.1 Wastewater. Obtain a representative sample of wastewater at
the inlet to the full-scale treatment plant if there is an existing
full-scale treatment plant (see section 6.3). If there is no existing
full-scale treatment plant, obtain the wastewater sample as close to
the point of determination as possible. Collect the sample by pumping
the wastewater into the 20-L collapsible container. The loss of
volatiles shall be minimized from the wastewater by collapsing the
container before filling, by minimizing the time of filling, and by
avoiding a headspace in the container after filling. If the wastewater
requires the addition of nutrients to support the biomass growth and
maintain biomass characteristics, those nutrients are added and mixed
with the container contents after the container is filled.
7.2 Biomass. Obtain the biomass or activated sludge used for rate
constant determination in the bench-scale process from the existing
full-scale process or from a representative biomass culture (e.g.,
biomass that has been developed for a future full-scale process). This
biomass is preferentially obtained from a thickened acclimated mixed
liquor sample. Collect the sample either by bailing from the mixed
liquor in the aeration tank with a weighted container, or by collecting
aeration tank effluent at the effluent overflow weir. Transport the
sample to the laboratory within no more than 4 hours of collection.
Maintain the biomass concentration in the benchtop bioreactor at the
level of the full-scale system +10 percent throughout the sampling
period of the test method.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Benchtop Bioreactor Operation. Charge the mixed liquor to the
benchtop bioreactor, minimizing headspace over the liquid surface to
minimize entrainment of mixed liquor in the circulating gas. Fasten the
benchtop bioreactor headplate to the reactor over the liquid surface.
Maintain the temperature of the contents of the benchtop bioreactor
system at the temperature of the target full-scale system,
2 deg.C, throughout the testing period. Monitor and record
the temperature of the benchtop bioreactor contents at least to the
nearest 0.1 deg.C.
8.1.1 Wastewater Storage. Collect the wastewater sample in the 20-
L collapsible container. Store the container at 4 deg.C throughout the
testing period. Connect the container to the benchtop bioreactor feed
pump.
8.1.2 Wastewater Flow Rate.
8.1.2.1 The hydraulic residence time of the aeration tank is
calculated as the ratio of the volume of the tank (L) to the flow rate
(L/min). At the beginning of a test, the container shall be connected
to the feed pump and solution shall be pumped to the benchtop
bioreactor at the required flow rate to achieve the calculated
hydraulic residence time of wastewater in the aeration tank.
[GRAPHIC] [TIFF OMITTED] TR17OC00.547

Where:

Qtest = wastewater flow rate (L/min)
Qfs = average flow rate of full-scale process (L/min)
Vfs = volume of full-scale aeration tank (L)

8.1.2.2 The target flow rate in the test apparatus is the same as
the flow rate in the target full-scale process

[[Page 62229]]

multiplied by the ratio of benchtop bioreactor volume (e.g., 6 L) to
the volume of the full-scale aeration tank. The hydraulic residence
time shall be maintained at 90 to 100 percent of the residence time
maintained in the full-scale unit. A nominal flow rate is set on the
pump based on a pump calibration. Changes in the elasticity of the
tubing in the pump head and the accumulation of material in the tubing
affect this calibration. The nominal pumping rate shall be changed as
necessary based on volumetric flow measurements. Discharge the benchtop
bioreactor effluent to a wastewater storage, treatment, or disposal
facility, except during sampling or flow measurement periods.
8.1.3 Sludge Recycle Rate. Set the sludge recycle rate at a rate
sufficient to prevent accumulation in the bottom of the clarifier. Set
the air circulation rate sufficient to maintain the biomass in
suspension.
8.1.4 Benchtop Bioreactor Operation and Maintenance. Temperature,
dissolved oxygen concentration, exit vent flow rate, benchtop
bioreactor effluent flow rate, and air circulation rate shall be
measured and recorded three times throughout each day of benchtop
bioreactor operation. If other parameters (such as pH) are measured and
maintained in the target full-scale unit, these parameters, where
appropriate, shall be monitored and maintained to target full-scale
specifications in the benchtop bioreactor. At the beginning of each
sampling period (Section 8.2), sample the benchtop bioreactor contents
for suspended solids analysis. Take this sample by loosening a clamp on
a length of tubing attached to the lower side port. Determine the
suspended solids gravimetrically by the Gooch crucible/glass fiber
filter method for total suspended solids, in accordance with Standard
Methods\3\ or equivalent. When necessary, sludge shall be wasted from
the lower side port of the benchtop bioreactor, and the volume that is
wasted shall be replaced with an equal volume of the reactor effluent.
Add thickened activated sludge mixed liquor as necessary to the
benchtop bioreactor to increase the suspended solids concentration to
the desired level. Pump this mixed liquor to the benchtop bioreactor
through the upper side port (Item 24 in Figure 304A-1). Change the
membrane on the dissolved oxygen probe before starting the test.
Calibrate the oxygen probe immediately before the start of the test and
each time the membrane is changed.
8.1.5 Inspection and Correction Procedures. If the feed line
tubing becomes clogged, replace with new tubing. If the feed flow rate
is not within 5 percent of target flow any time the flow rate is
measured, reset pump or check the flow measuring device and measure
flow rate again until target flow rate is achieved.
8.2 Test Sampling. At least two and one half hydraulic residence
times after the system has reached the targeted specifications shall be
permitted to elapse before the first sample is taken. Effluent samples
of the clarifier discharge (Item 20 in Figure 304A-1) and the influent
wastewater feed are collected in 40-mL septum vials to which two drops
of 1:10 hydrochloric acid (HCl) in water have been added. Sample the
clarifier discharge directly from the drain line. These samples will be
composed of the entire flow from the system for a period of several
minutes. Feed samples shall be taken from the feed pump suction line
after temporarily stopping the benchtop bioreactor feed, removing a
connector, and squeezing the collapsible feed container. Store both
influent and effluent samples at 4 deg.C immediately after collection
and analyze within 8 hours of collection.
8.2.1 Frequency of Sampling. During the test, sample and analyze
the wastewater feed and the clarifier effluent at least six times. The
sampling intervals shall be separated by at least 8 hours. During any
individual sampling interval, sample the wastewater feed simultaneously
with or immediately after the effluent sample. Calculate the relative
standard deviation (RSD) of the amount removed (i.e., effluent
concentration--wastewater feed concentration). The RSD values shall be
15 percent. If an RSD value is > 15 percent, continue sampling and
analyzing influent and effluent sets of samples until the RSD values
are within specifications.
8.2.2 Sampling After Exposure of System to Atmosphere. If, after
starting sampling procedures, the benchtop bioreactor system is exposed
to the atmosphere (due to leaks, maintenance, etc.), allow at least one
hydraulic residence time to elapse before resuming sampling.

9.0 Quality Control

9.1 Dissolved Oxygen. Fluctuation in dissolved oxygen
concentration may occur for numerous reasons, including undetected gas
leaks, increases and decreases in mixed liquor suspended solids
resulting from cell growth and solids loss in the effluent stream,
changes in diffuser performance, cycling of effluent flow rate, and
overcorrection due to faulty or sluggish dissolved oxygen probe
response. Control the dissolved oxygen concentration in the benchtop
bioreactor by changing the proportion of oxygen in the circulating
aeration gas. Should the dissolved oxygen concentration drift below the
designated experimental condition, bleed a small amount of aeration gas
from the system on the pressure side (i.e., immediately upstream of one
of the diffusers). This will create a vacuum in the system, triggering
the pressure sensitive relay to open the solenoid valve and admit
oxygen to the system. Should the dissolved oxygen concentration drift
above the designated experimental condition, slow or stop the oxygen
input to the system until the dissolved oxygen concentration approaches
the correct level.
9.2 Sludge Wasting.
9.2.1 Determine the suspended solids concentration (section 8.1.4)
at the beginning of a test, and once per day thereafter during the
test. If the test is completed within a two day period, determine the
suspended solids concentration after the final sample set is taken. If
the suspended solids concentration exceeds the specified concentration,
remove a fraction of the sludge from the benchtop bioreactor. The
required volume of mixed liquor to remove is determined as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.548

Where:

Vw is the wasted volume (Liters),
Vr is the volume of the benchtop bioreactor (Liters),
Sm is the measured solids (g/L), and
Ss is the specified solids (g/L).

[[Page 62230]]

wasted. Replace the volume of the liquid wasted by pouring the same
volume of effluent back into the benchtop bioreactor. Dispose of the
waste sludge properly.
9.3 Sludge Makeup. In the event that the suspended solids
concentration is lower than the specifications, add makeup sludge back
into the benchtop bioreactor. Determine the amount of sludge added by
the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.549

Where:

Vw is the volume of sludge to add (Liters),
Vr is the volume of the benchtop bioreactor (Liters),
Sw is the solids in the makeup sludge (g/L),
Sm is the measured solids (g/L), and Ss is the
specified solids (g/L).

10.0 Calibration and Standardization

10.1 Wastewater Pump Calibration. Determine the wastewater flow
rate by collecting the system effluent for a time period of at least
one hour, and measuring the volume with a graduated cylinder. Record
the collection time period and volume collected. Determine flow rate.
Adjust the pump speed to deliver the specified flow rate.
10.2 Calibration Standards. Prepare calibration standards from
pure certified standards in an aqueous medium. Prepare and analyze
three concentrations of calibration standards for each target component
(or for a mixture of components) in triplicate daily throughout the
analyses of the test samples. At each concentration level, a single
calibration shall be within 5 percent of the average of the three
calibration results. The low and medium calibration standards shall
bracket the expected concentration of the effluent (treated)
wastewater. The medium and high standards shall bracket the expected
influent concentration.

11.0 Analytical Procedures

11.1 Analysis. If the identity of the compounds of interest in the
wastewater is not known, a representative sample of the wastewater
shall be analyzed in order to identify all of the compounds of interest
present. A gas chromatography/mass spectrometry screening method is
recommended.
11.1.1 After identifying the compounds of interest in the
wastewater, develop and/or use one or more analytical techniques
capable of measuring each of those compounds (more than one analytical
technique may be required, depending on the characteristics of the
wastewater). Test Method 18, found in appendix A of 40 CFR 60, may be
used as a guideline in developing the analytical technique. Purge and
trap techniques may be used for analysis providing the target
components are sufficiently volatile to make this technique
appropriate. The limit of quantitation for each compound shall be
determined (see reference 1). If the effluent concentration of any
target compound is below the limit of quantitation determined for that
compound, the operation of the Method 304 unit may be altered to
attempt to increase the effluent concentration above the limit of
quantitation. Modifications to the method shall be approved prior to
the test. The request should be addressed to Method 304 contact,
Emissions Measurement Center, Mail Drop 19, U.S. Environmental
Protection Agency, Research Triangle Park, NC 27711.

12.0 Data Analysis and Calculations

12.1 Nomenclature. The following symbols are used in the
calculations.

Ci = Average inlet feed concentration for a compound of
interest, as analyzed (mg/L)
Co = Average outlet (effluent) concentration for a compound
of interest, as analyzed (mg/L)
X = Biomass concentration, mixed liquor suspended solids (g/L)
t = Hydraulic residence time in the benchtop bioreactor (hours)
V = Volume of the benchtop bioreactor (L)
Q = Flow rate of wastewater into the benchtop bioreactor, average (L/
hour)

12.2 Residence Time. The hydraulic residence time of the benchtop
bioreactor is equal to the ratio of the volume of the benchtop
bioreactor (L) to the flow rate (L/h):
[GRAPHIC] [TIFF OMITTED] TR17OC00.550

12.3 Rate of Biodegradation. Calculate the rate of biodegradation
for each component with the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.551

12.4 First-Order Biorate Constant. Calculate the first-order
biorate constant (K1) for each component with the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.552

12.5 Relative Standard Deviation (RSD). Determine the standard
deviation of both the influent and effluent sample concentrations (S)
using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.553

[[Page 62231]]

12.6 Determination of Percent Air Emissions and Percent
Biodegraded. Use the results from this test method and follow the
applicable procedures in appendix C of 40 CFR part 63, entitled,
``Determination of the Fraction Biodegraded (Fbio) in a
Biological Treatment Unit'' to determine Fbio.

13.0 Method Performance, [Reserved]

14.0 Pollution Prevention, [Reserved]

15.0 Waste Management, [Reserved]

16.0 References

1. ``Guidelines for data acquisition and data quality evaluation
in Environmental Chemistry,'' Daniel MacDoughal, Analytical
Chemistry, Volume 52, p. 2242, 1980.
2. Test Method 18, 40 CFR 60, appendix A.
3. Standard Methods for the Examination of Water and Wastewater,
16th Edition, Method 209C, Total Suspended Solids Dried at 103-105
deg.C, APHA, 1985.
4. Water7, Hazardous Waste Treatment, Storage, and Disposal
Facilities (TSDF)--Air Emission Models, U.S. Environmental
Protection Agency, EPA-450/3-87-026, Review Draft, November 1989.
5. Chemdat7, Hazardous Waste Treatment, Storage, and Disposal
Facilities (TSDF)--Air Emission Models, U.S. Environmental
Protection Agency, EPA-450/3-87-026, Review Draft, November 1989.

[[Page 62232]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.554

[[Page 62233]]

Method 304B: Determination of Biodegradation Rates of Organic
Compounds (Scrubber Option)

1.0 Scope and Application

1.1 Applicability. This method is applicable for the determination
of biodegradation rates of organic compounds in an activated sludge
process. The test method is designed to evaluate the ability of an
aerobic biological reaction system to degrade or destroy specific
components in waste streams. The method may also be used to determine
the effects of changes in wastewater composition on operation. The
biodegradation rates determined by utilizing this method are not
representative of a full-scale system. Full-scale systems embody
biodegradation and air emissions in competing reactions. This method
measures biodegradation in absence of air emissions. The rates measured
by this method shall be used in conjunction with the procedures listed
in appendix C of this part to calculate the fraction emitted to the air
versus the fraction biodegraded.

2.0 Summary of Method

2.1 A self-contained benchtop bioreactor system is assembled in
the laboratory. A sample of mixed liquor is added and the waste stream
is then fed continuously. The benchtop bioreactor is operated under
conditions nearly identical to the target full-scale activated sludge
process, except that air emissions are not a factor. The benchtop
bioreactor temperature, dissolved oxygen concentration, average
residence time in the reactor, waste composition, biomass
concentration, and biomass composition of the target full-scale process
are the parameters which are duplicated in the laboratory system.
Biomass shall be removed from the target full-scale activated sludge
unit and held for no more than 4 hours prior to use in the benchtop
bioreactor. If antifoaming agents are used in the full-scale system,
they shall also be used in the benchtop bioreactor. The feed flowing
into and the effluent exiting the benchtop bioreactor are analyzed to
determine the biodegradation rates of the target compounds. The choice
of analytical methodology for measuring the compounds of interest at
the inlet and outlet to the benchtop bioreactor are left to the
discretion of the source, except where validated methods are available.

3.0 Definitions. [Reserved]

4.0 Interferences. [Reserved]

5.0 Safety

6.0 Equipment and Supplies

Note: Figure 304B-1 illustrates a typical laboratory apparatus
used to measure biodegradation rates. While the following
description refers to Figure 304B-1, the EPA recognizes that
alternative reactor configurations, such as alternative reactor
shapes and locations of probes and the feed inlet, will also meet
the intent of this method. Ensure that the benchtop bioreactor
system is self-contained and isolated from the atmosphere by leak-
checking fittings, tubing, etc.

6.1 Benchtop Bioreactor. The biological reaction is conducted in a
biological oxidation reactor of at least 6-liters capacity. The
benchtop bioreactor is sealed and equipped with internal probes for
controlling and monitoring dissolved oxygen and internal temperature.
The top of the benchtop bioreactor is equipped for aerators, gas flow
ports, and instrumentation (while ensuring that no leaks to the
atmosphere exist around the fittings).
6.2 Aeration gas. Aeration gas is added to the benchtop bioreactor
through three diffusers, which are glass tubes that extend to the
bottom fifth of the reactor depth. A pure oxygen pressurized cylinder
is recommended in order to maintain the specified oxygen concentration.
Install a blower (e.g., Diaphragm Type, 15 SCFH capacity) to blow the
aeration gas into the benchtop bioreactor diffusers. Measure the
aeration gas flow rate with a rotameter (e.g., 0-15 SCFH recommended).
The aeration gas will rise through the benchtop bioreactor, dissolving
oxygen into the mixture in the process. The aeration gas must provide
sufficient agitation to keep the solids in suspension. Provide an exit
for the aeration gas from the top flange of the benchtop bioreactor
through a water-cooled (e.g., Allihn-type) vertical condenser. Install
the condenser through a gas-tight fitting in the benchtop bioreactor
closure. Design the system so that at least 10 percent of the gas flows
through an alkaline scrubber containing 175 mL of 45 percent by weight
solution of potassium hydroxide (KOH) and 5 drops of 0.2 percent
alizarin yellow dye. Route the balance of the gas through an adjustable
scrubber bypass. Route all of the gas through a 1-L knock-out flask to
remove entrained moisture and then to the intake of the blower. The
blower recirculates the gas to the benchtop bioreactor.
6.3 Wastewater Feed. Supply the wastewater feed to the benchtop
bioreactor in a collapsible low-density polyethylene container or
collapsible liner in a container (e.g., 20 L) equipped with a spigot
cap (collapsible containers or liners of other material may be required
due to the permeability of some volatile compounds through
polyethylene). Obtain the wastewater feed by sampling the wastewater
feed in the target process. A representative sample of wastewater shall
be obtained from the piping leading to the aeration tank. This sample
may be obtained from existing sampling valves at the discharge of the
wastewater feed pump, or collected from a pipe discharging to the
aeration tank, or by pumping from a well-mixed equalization tank
upstream from the aeration tank. Alternatively, wastewater can be
pumped continuously to the laboratory apparatus from a bleed stream
taken from the equalization tank of the full-scale treatment system.
6.3.1 Refrigeration System. Keep the wastewater feed cool by ice
or by refrigeration to 4 deg.C. If using a bleed stream from the
equalization tank, refrigeration is not required if the residence time
in the bleed stream is less than five minutes.
6.3.2 Wastewater Feed Pump. The wastewater is pumped from the
refrigerated container using a variable-speed peristaltic pump drive
equipped with a peristaltic pump head. Add the feed solution to the
benchtop bioreactor through a fitting on the top flange. Determine the
rate of feed addition to provide a retention time in the benchtop
bioreactor that is numerically equivalent to the retention time in the
target full-scale system. The wastewater shall be fed at a rate
sufficient to achieve 90 to 100 percent of the target full-scale system
residence time.
6.3.3 Treated wastewater feed. The benchtop bioreactor effluent
exits at the bottom of the reactor through a tube and proceeds to the
clarifier.
6.4 Clarifier. The effluent flows to a separate closed clarifier
that allows separation of biomass and effluent (e.g., 2-liter pear-
shaped glass separatory funnel, modified by removing the stopcock and
adding a 25-mm OD glass tube at the bottom). Benchtop bioreactor
effluent enters the clarifier through a tube inserted to a depth of
0.08 m (3 in.)

[[Page 62234]]

through a stopper at the top of the clarifier. System effluent flows
from a tube inserted through the stopper at the top of the clarifier to
a drain (or sample bottle when sampling). The underflow from the
clarifier leaves from the glass tube at the bottom of the clarifier.
Flexible tubing connects this fitting to the sludge recycle pump. This
pump is coupled to a variable speed pump drive. The discharge from this
pump is returned through a tube inserted in a port on the side of the
benchtop bioreactor. An additional port is provided near the bottom of
the benchtop bioreactor for sampling the reactor contents. The mixed
liquor from the benchtop bioreactor flows into the center of the
clarifier. The clarified system effluent separates from the biomass and
flows through an exit near the top of the clarifier. There shall be no
headspace in the clarifier.
6.5 Temperature Control Apparatus. Capable of maintaining the
system at a temperature equal to the temperature of the full-scale
system. The average temperature should be maintained within
2 deg.C of the set point.
6.5.1 Temperature Monitoring Device. A resistance type temperature
probe or a thermocouple connected to a temperature readout with a
resolution of 0.1 deg.C or better.
6.5.2 Benchtop Bioreactor Heater. The heater is connected to the
temperature control device.
6.6 Oxygen Control System. Maintain the dissolved oxygen
concentration at the levels present in the full-scale system. Target
full-scale activated sludge systems with dissolved oxygen concentration
below 2 mg/L are required to maintain the dissolved oxygen
concentration in the benchtop bioreactor within 0.5 mg/L of the target
dissolved oxygen level. Target full-scale activated sludge systems with
dissolved oxygen concentration above 2 mg/L are required to maintain
the dissolved oxygen concentration in the benchtop bioreactor within
1.5 mg/L of the target dissolved oxygen concentration; however, for
target full-scale activated sludge systems with dissolved oxygen
concentrations above 2 mg/L, the dissolved oxygen concentration in the
benchtop bioreactor may not drop below 1.5 mg/L. If the benchtop
bioreactor is outside the control range, the dissolved oxygen is noted
and the reactor operation is adjusted.
6.6.1 Dissolved Oxygen Monitor. Dissolved oxygen is monitored with
a polarographic probe (gas permeable membrane) connected to a dissolved
oxygen meter (e.g., 0 to 15 mg/L, 0 to 50 deg.C).
6.6.2 Benchtop Bioreactor Pressure Monitor. The benchtop
bioreactor pressure is monitored through a port in the top flange of
the reactor. This is connected to a gauge control with a span of 13-cm
water vacuum to 13-cm water pressure or better. A relay is activated
when the vacuum exceeds an adjustable setpoint which opens a solenoid
valve (normally closed), admitting oxygen to the system. The vacuum
setpoint controlling oxygen addition to the system shall be set at
approximately 2.5 0.5 cm water and maintained at this
setting except during brief periods when the dissolved oxygen
concentration is adjusted.
6.7 Connecting Tubing. All connecting tubing shall be Teflon or
equivalent in impermeability. The only exception to this specification
is the tubing directly inside the pump head of the wastewater feed
pump, which may be Viton, Silicone or another type of flexible tubing.

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

7.0. Reagents and Standards

7.1 Wastewater. Obtain a representative sample of wastewater at
the inlet to the full-scale treatment plant if there is an existing
full-scale treatment plant (See Section 6.3). If there is no existing
full-scale treatment plant, obtain the wastewater sample as close to
the point of determination as possible. Collect the sample by pumping
the wastewater into the 20-L collapsible container. The loss of
volatiles shall be minimized from the wastewater by collapsing the
container before filling, by minimizing the time of filling, and by
avoiding a headspace in the container after filling. If the wastewater
requires the addition of nutrients to support the biomass growth and
maintain biomass characteristics, those nutrients are added and mixed
with the container contents after the container is filled.
7.2 Biomass. Obtain the biomass or activated sludge used for rate
constant determination in the bench-scale process from the existing
full-scale process or from a representative biomass culture (e.g.,
biomass that has been developed for a future full-scale process). This
biomass is preferentially obtained from a thickened acclimated mixed
liquor sample. Collect the sample either by bailing from the mixed
liquor in the aeration tank with a weighted container, or by collecting
aeration tank effluent at the effluent overflow weir. Transport the
sample to the laboratory within no more than 4 hours of collection.
Maintain the biomass concentration in the benchtop bioreactor at the
level of the target full-scale system +10 percent throughout the
sampling period of the test method.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Benchtop Bioreactor Operation. Charge the mixed liquor to the
benchtop bioreactor, minimizing headspace over the liquid surface to
minimize entrainment of mixed liquor in the circulating gas. Fasten the
benchtop bioreactor headplate to the reactor over the liquid surface.
Maintain the temperature of the contents of the benchtop bioreactor
system at the temperature of the target full-scale system,
2 deg.C, throughout the testing period. Monitor and record
the temperature of the reactor contents at least to the nearest
0.1 deg.C.
8.1.1 Wastewater Storage. Collect the wastewater sample in the 20-
L collapsible container. Store the container at 4 deg.C throughout the
testing period. Connect the container to the benchtop bioreactor feed
pump.
8.1.2 Wastewater Flow Rate.
8.1.2.1 The hydraulic residence time of the aeration tank is
calculated as the ratio of the volume of the tank (L) to the flow rate
(L/min). At the beginning of a test, the container shall be connected
to the feed pump and solution shall be pumped to the benchtop
bioreactor at the required flow rate to achieve the calculated
hydraulic residence time of wastewater in the aeration tank.
[GRAPHIC] [TIFF OMITTED] TR17OC00.555

Where:

Qtest = wastewater flow rate (L/min)
Qfs = average flow rate of full-scale process (L/min)
Vfs = volume of full-scale aeration tank (L)

[[Page 62235]]

8.1.2.2 The target flow rate in the test apparatus is the same as
the flow rate in the target full-scale process multiplied by the ratio
of benchtop bioreactor volume (e.g., 6 L) to the volume of the full-
scale aeration tank. The hydraulic residence time shall be maintained
at 90 to 100 percent of the residence time maintained in the target
full-scale unit. A nominal flow rate is set on the pump based on a pump
calibration. Changes in the elasticity of the tubing in the pump head
and the accumulation of material in the tubing affect this calibration.
The nominal pumping rate shall be changed as necessary based on
volumetric flow measurements. Discharge the benchtop bioreactor
effluent to a wastewater storage, treatment, or disposal facility,
except during sampling or flow measurement periods.
8.1.3 Sludge Recycle Rate. Set the sludge recycle rate at a rate
sufficient to prevent accumulation in the bottom of the clarifier. Set
the air circulation rate sufficient to maintain the biomass in
suspension.
8.1.4 Benchtop Bioreactor Operation and Maintenance. Temperature,
dissolved oxygen concentration, flow rate, and air circulation rate
shall be measured and recorded three times throughout each day of
testing. If other parameters (such as pH) are measured and maintained
in the target full-scale unit, these parameters shall, where
appropriate, be monitored and maintained to full-scale specifications
in the benchtop bioreactor. At the beginning of each sampling period
(section 8.2), sample the benchtop bioreactor contents for suspended
solids analysis. Take this sample by loosening a clamp on a length of
tubing attached to the lower side port. Determine the suspended solids
gravimetrically by the Gooch crucible/glass fiber filter method for
total suspended solids, in accordance with Standard Methods3
or equivalent. When necessary, sludge shall be wasted from the lower
side port of the benchtop bioreactor, and the volume that is wasted
shall be replaced with an equal volume of the benchtop bioreactor
effluent. Add thickened activated sludge mixed liquor as necessary to
the benchtop bioreactor to increase the suspended solids concentration
to the desired level. Pump this mixed liquor to the benchtop bioreactor
through the upper side port (Item 24 in Figure 304B-1). Change the
membrane on the dissolved oxygen probe before starting the test.
Calibrate the oxygen probe immediately before the start of the test and
each time the membrane is changed. The scrubber solution shall be
replaced each weekday with 175 mL 45 percent W/W KOH solution to which
five drops of 0.2 percent alizarin yellow indicator in water have been
added. The potassium hydroxide solution in the alkaline scrubber shall
be changed if the alizarin yellow dye color changes.
8.1.5 Inspection and Correction Procedures. If the feed line
tubing becomes clogged, replace with new tubing. If the feed flow rate
is not within 5 percent of target flow any time the flow rate is
measured, reset pump or check the flow measuring device and measure
flow rate again until target flow rate is achieved.
8.2 Test Sampling. At least two and one half hydraulic residence
times after the system has reached the targeted specifications shall be
permitted to elapse before the first sample is taken. Effluent samples
of the clarifier discharge (Item 20 in Figure 304B-1) and the influent
wastewater feed are collected in 40-mL septum vials to which two drops
of 1:10 hydrochloric acid (HCl) in water have been added. Sample the
clarifier discharge directly from the drain line. These samples will be
composed of the entire flow from the system for a period of several
minutes. Feed samples shall be taken from the feed pump suction line
after temporarily stopping the benchtop bioreactor feed, removing a
connector, and squeezing the collapsible feed container. Store both
influent and effluent samples at 4 deg.C immediately after collection
and analyze within 8 hours of collection.
8.2.1 Frequency of Sampling. During the test, sample and analyze
the wastewater feed and the clarifier effluent at least six times. The
sampling intervals shall be separated by at least 8 hours. During any
individual sampling interval, sample the wastewater feed simultaneously
with or immediately after the effluent sample. Calculate the RSD of the
amount removed (i.e., effluent concentration--wastewater feed
concentration). The RSD values shall be 15 percent. If an RSD value is
>15 percent, continue sampling and analyzing influent and effluent sets
of samples until the RSD values are within specifications.
8.2.2 Sampling After Exposure of System to Atmosphere. If, after
starting sampling procedures, the benchtop bioreactor system is exposed
to the atmosphere (due to leaks, maintenance, etc.), allow at least one
hydraulic residence time to elapse before resuming sampling.

9.0 Quality Control

[[Page 62236]]

Where:

Vw is the wasted volume (Liters),
Vr is the volume of the benchtop bioreactor (Liters),
Sm is the measured solids (g/L), and
Ss is the specified solids (g/L).

9.2.2 Remove the mixed liquor from the benchtop bioreactor by
loosening a clamp on the mixed liquor sampling tube and allowing the
required volume to drain to a graduated flask. Clamp the tube when the
correct volume has been wasted. Replace the volume of the liquid wasted
by pouring the same volume of effluent back into the benchtop
bioreactor. Dispose of the waste sludge properly.
9.3 Sludge Makeup. In the event that the suspended solids
concentration is lower than the specifications, add makeup sludge back
into the benchtop bioreactor. Determine the amount of sludge added by
the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.557

Where:

10.0 Calibration and Standardizations

11.0 Analytical Test Procedures

11.1 Analysis. If the identity of the compounds of interest in the
wastewater is not known, a representative sample of the wastewater
shall be analyzed in order to identify all of the compounds of interest
present. A gas chromatography/mass spectrometry screening method is
recommended.
11.1.1 After identifying the compounds of interest in the
wastewater, develop and/or use one or more analytical technique capable
of measuring each of those compounds (more than one analytical
technique may be required, depending on the characteristics of the
wastewater). Method 18, found in appendix A of 40 CFR 60, may be used
as a guideline in developing the analytical technique. Purge and trap
techniques may be used for analysis providing the target components are
sufficiently volatile to make this technique appropriate. The limit of
quantitation for each compound shall be determined.\1\ If the effluent
concentration of any target compound is below the limit of quantitation
determined for that compound, the operation of the Method 304 unit may
be altered to attempt to increase the effluent concentration above the
limit of quantitation. Modifications to the method shall be approved
prior to the test. The request should be addressed to Method 304
contact, Emissions Measurement Center, Mail Drop 19, U.S. Environmental
Protection Agency, Research Triangle Park, NC 27711.

12.0 Data Analysis and Calculations

12.1 Nomenclature. The following symbols are used in the
calculations.

12.2 Residence Time. The hydraulic residence time of the benchtop
bioreactor is equal to the ratio of the volume of the benchtop
bioreactor (L) to the flow rate (L/h)
[GRAPHIC] [TIFF OMITTED] TR17OC00.558

12.3 Rate of Biodegradation. Calculate the rate of biodegradation
for each component with the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.559

12.4 First-Order Biorate Constant. Calculate the first-order
biorate constant (K1) for each component with the following equation:

[[Page 62237]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.560

12.6 Determination of Percent Air Emissions and Percent
Biodegraded. Use the results from this test method and follow the
applicable procedures in appendix C of 40 CFR Part 63, entitled,
``Determination of the Fraction Biodegraded (Fbio) in a
Biological Treatment Unit'' to determine Fbio.

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. ``Guidelines for data acquisition and data quality evaluation
in Environmental Chemistry'', Daniel MacDoughal, Analytical
Chemistry, Volume 52, p. 2242, 1980.
2. Test Method 18, 40 CFR 60, Appendix A.
3. Standard Methods for the Examination of Water and Wastewater,
16th Edition, Method 209C, Total Suspended Solids Dried at 103-
105 deg.C, APHA, 1985.
4. Water--7, Hazardous Waste Treatment, Storage, and Disposal
Facilities (TSDF)--Air Emission Models, U.S. Environmental
Protection Agency, EPA-450/3-87-026, Review Draft, November 1989.
5. Chemdat7, Hazardous Waste Treatment, Storage, and Disposal
Facilities (TSDF)--Air Emission Models, U.S. Environmental
Protection Agency, EPA-450/3-87-026, Review Draft, November 1989.
BILLING CODE 6560-50-P

[[Page 62238]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.562

BILLING CODE 6560-50-C

[[Page 62239]]

Method 305: Measurement of Emission Potential of Individual
Volatile Organic Compounds in Waste

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 40 CFR Part 60,
Appendix A. Therefore, to obtain reliable results, persons using
this method should have a thorough knowledge of at least Method 25D.

1.0 Scope and Application

1.1 Analyte. Volatile Organics. No CAS No. assigned.
1.2 Applicability. This procedure is used to determine the
emission potential of individual volatile organics (VOs) in waste.
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 heated purge conditions established by Method 25D (40 CFR
Part 60, Appendix A) are used to remove VOs from a 10 gram sample of
waste suspended in a 50/50 solution of polyethylene glycol (PEG) and
water. The purged VOs are quantified by using the sample collection and
analytical techniques (e.g. gas chromatography) appropriate for the VOs
present in the waste. The recovery efficiency of the sample collection
and analytical technique is determined for each waste matrix. A
correction factor is determined for each compound (if acceptable
recovery criteria requirements are met of 70 to 130 percent recovery
for every target compound), and the measured waste concentration is
corrected with the correction factor for each compound. A minimum of
three replicate waste samples shall be analyzed.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

6.1 Method 25D Purge Apparatus.
6.1.1 Purge Chamber. The purge chamber shall accommodate the 10
gram sample of waste suspended in a matrix of 50 mL of PEG and 50 mL of
deionized, hydrocarbon-free water. Three fittings are used on the glass
chamber top. Two #7 Ace-threads are used for the purge gas inlet and
outlet connections. A #50 Ace-thread is used to connect the top of the
chamber to the base (see Figure 305-1). The base of the chamber has a
side-arm equipped with a #22 Sovirel fitting to allow for easy sample
introductions into the chamber. The dimensions of the chamber are shown
in Figure 305-1.
6.1.2 Flow Distribution Device (FDD). The FDD enhances the gas-to-
liquid contact for improved purging efficiency. The FDD is a 6 mm OD
(0.2 in) by 30 cm (12 in) long glass tube equipped with four arm
bubblers as shown in Figure 305-1. Each arm shall have an opening of 1
mm (0.04 in) in diameter.
6.1.3 Coalescing Filter. The coalescing filter serves to
discourage aerosol formation of sample gas once it leaves the purge
chamber. The glass filter has a fritted disc mounted 10 cm (3.9 in)
from the bottom. Two #7 Ace-threads are used for the inlet and outlet
connections. The dimensions of the chamber are shown in Figure 305-2.
6.1.4 Oven. A forced convection airflow oven capable of
maintaining the purge chamber and coalescing filter at 75
2 deg.C (167 3.6 deg.F).
6.1.5 Toggle Valve. An on/off valve constructed from brass or
stainless steel rated to 100 psig. This valve is placed in line between
the purge nitrogen source and the flow controller.
6.1.6 Flow Controller. High-quality stainless steel flow
controller capable of restricting a flow of nitrogen to 6
0.06 L/min (0.2 0.002 ft3/min) at 40 psig.
6.1.7 Polyethylene Glycol Cleaning System.
6.1.7.1 Round-Bottom Flask. One liter, three-neck glass round-
bottom flask for cleaning PEG. Standard taper 24/40 joints are mounted
on each neck.
6.1.7.2 Heating Mantle. Capable of heating contents of the 1-L
flask to 120 deg.C (248 deg.F).
6.1.7.3 Nitrogen Bubbler. Teflon or glass tube, 0.25 in
OD (6.35 mm).
6.1.7.4 Temperature Sensor. Partial immersion glass thermometer.
6.1.7.5 Hose Adapter. Glass with 24/40 standard tapered joint.
6.2 Volatile Organic Recovery System.
6.2.1 Splitter Valve (Optional). Stainless steel cross-pattern
valve capable of splitting nominal flow rates from the purge flow of 6
L/min (0.2 ft3/min). The valve shall be maintained at 75 +
2 deg.C (167 3.6 deg.F) in the heated zone and shall be
placed downstream of the coalescing filter. It is recommended that
0.125 in OD (3.175 mm) tubing be used to direct the split vent flow
from the heated zone. The back pressure caused by the 0.125 in OD
(3.175 mm) tubing is critical for maintaining proper split valve
operation.

Note: The splitter valve design is optional; it may be used in
cases where the concentration of a pollutant would saturate the
adsorbents.

6.2.2 Injection Port. Stainless steel 1/4 in OD (6.35 mm)
compression fitting tee with a 6 mm (0.2 in) septum fixed on the top
port. The injection port is the point of entry for the recovery study
solution. If using a gaseous standard to determine recovery efficiency,
connect the gaseous standard to the injection port of the tee.
6.2.3 Knockout Trap (Optional but Recommended). A 25 mL capacity
glass reservoir body with a full-stem impinger (to avoid leaks, a
modified midget glass impinger with a screw cap and ball/socket clamps
on the inlet and outlet is recommended). The empty impinger is placed
in an ice water bath between the injection port and the sorbent
cartridge. Its purpose is to reduce the water content of the purge gas
(saturated at 75 deg.C (167 deg.F)) before the sorbent cartridge.
6.2.4 Insulated Ice Bath. A 350 mL dewar or other type of
insulated bath is used to maintain ice water around the knockout trap.
6.2.5 Sorbent Cartridges. Commercially available glass or
stainless steel cartridge packed with one or more appropriate sorbents.
The amount of adsorbent packed in the cartridge depends on the
breakthrough volume of the test compounds but is limited by back
pressure caused by the packing (not to exceed 7 psig). More than one
sorbent cartridge placed in series may be necessary depending upon the
mixture of the measured components.
6.2.6 Volumetric Glassware. Type A glass 10 mL volumetric flasks
for measuring a final volume from the water catch in the knockout trap.
6.2.7 Thermal Desorption Unit. A clam-shell type oven, used for
the desorption of direct thermal desorption sorbent tubes. The oven
shall be capable of increasing the temperature of the desorption tubes
rapidly to recommended desorption temperature.
6.2.8 Ultrasonic Bath. Small bath used to agitate sorbent material
and desorption solvent. Ice water shall be used in the bath because of
heat transfer caused by operation of the bath.

[[Page 62240]]

6.2.9 Desorption Vials. Four-dram (15 mL) capacity borosilicate
glass vials with Teflon-lined caps.
6.3 Analytical System. A gas chromatograph (GC) is commonly used
to separate and quantify compounds from the sample collection and
recovery procedure. Method 18 (40 CFR Part 60, Appendix A) may be used
as a guideline for determining the appropriate GC column and GC
detector based on the test compounds to be determined. Other types of
analytical instrumentation may be used (HPLC) in lieu of GC systems as
long as the recovery efficiency criteria of this method are met.
6.3.1 Gas Chromatograph (GC). The GC shall be equipped with a
constant-temperature liquid injection port or a heated sampling loop/
valve system, as appropriate. The GC oven shall be temperature-
programmable over the useful range of the GC column. The choice of
detectors is based on the test compounds to be determined.
6.3.2 GC Column. Select the appropriate GC column based on (1)
literature review or previous experience, (2) polarity of the analytes,
(3) capacity of the column, or (4) resolving power (e.g., length,
diameter, film thickness) required.
6.3.3 Data System. A programmable electronic integrator for
recording, analyzing, and storing the signal generated by the detector.

7.0 Reagents and Standards

7.1 Method 25D Purge Apparatus.
7.1.1 Polyethylene Glycol (PEG). Ninety-eight percent pure organic
polymer with an average molecular weight of 400 g/mol. Volatile
organics are removed from the PEG prior to use by heating to 120
5 deg.C (248 9 deg.F) and purging with pure
nitrogen at 1 L/min (0.04 ft3/min) for 2 hours. After
purging and heating, the PEG is maintained at room temperature under a
nitrogen purge maintained at 1 L/min (0.04 ft3/min) until
used. A typical apparatus used to clean the PEG is shown in Figure 305-
3.
7.1.2 Water. Organic-free deionized water is required.
7.1.3 Nitrogen. High-purity nitrogen (less than 0.5 ppm total
hydrocarbons) is used to remove test compounds from the purge matrix.
The source of nitrogen shall be regulated continuously to 40 psig
before the on/off toggle valve.
7.2 Volatile Organic Recovery System.
7.2.1 Water. Organic-free deionized water is required.
7.2.2 Desorption Solvent (when used). Appropriate high-purity
(99.99 percent) solvent for desorption shall be used. Analysis shall be
performed (utilizing the same analytical technique as that used in the
analysis of the waste samples) on each lot to determine purity.
7.3 Analytical System. The gases required for GC operation shall
be of the highest obtainable purity (hydrocarbon free). Consult the
operating manual for recommended settings.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Assemble the glassware and associated fittings (see Figures
305-3 and 305-4, as appropriate) and leak-check the system
(approximately 7 psig is the target pressure). After an initial leak
check, mark the pressure gauge and use the initial checkpoint to
monitor for leaks throughout subsequent analyses. If the pressure in
the system drops below the target pressure at any time during analysis,
that analysis shall be considered invalid.
8.2 Recovery Efficiency Determination. Determine the individual
recovery efficiency (RE) for each of the target compounds in duplicate
before the waste samples are analyzed. To determine the RE, generate a
water blank (Section 11.1) and use the injection port to introduce a
known volume of spike solution (or certified gaseous standard)
containing all of the target compounds at the levels expected in the
waste sample. Introduce the spike solution immediately after the
nitrogen purge has been started (Section 8.3.2). Follow the procedures
outlined in Section 8.3.3. Analyze the recovery efficiency samples
using the techniques described in Section 11.2. Determine the recovery
efficiency (Equation 305-1, Section 12.2) by comparing the amount of
compound recovered to the theoretical amount spiked. Determine the RE
twice for each compound; the relative standard deviation, (RSD) shall
be 10 percent for each compound. If the RSD for any
compound is not 10 percent, modify the sampling/analytical
procedure and complete an RE study in duplicate, or continue
determining RE until the RSD meets the acceptable criteria. The average
RE shall be 0.70 RE 1.30 for each compound. If
the average RE does not meet these criteria, an alternative sample
collection and/or analysis technique shall be developed and the
recovery efficiency determination shall be repeated for that compound
until the criteria are met for every target compound. Example
modifications of the sampling/analytical system include changing the
adsorbent material, changing the desorption solvent, utilizing direct
thermal desorption of test compounds from the sorbent tubes, utilizing
another analytical technique.
8.3 Sample Collection and Recovery.
8.3.1 The sample collection procedure in Method 25D shall be used
to collect (into a preweighed vial) 10 g of waste into PEG, cool, and
ship to the laboratory. Remove the sample container from the cooler and
wipe the exterior to remove any ice or water. Weigh the container and
sample to the nearest 0.01 g and record the weight. Pour the sample
from the container into the purge flask. Rinse the sample container
three times with approximately 6 mL of PEG (or the volume needed to
total 50 mL of PEG in the purge flask), transferring the rinses to the
purge flask. Add 50 mL of organic-free deionized water to the purge
flask. Cap the purge flask tightly in between each rinse and after
adding all the components into the flask.
8.3.2 Allow the oven to equilibrate to 75 2 deg.C
(167 3.6 deg.F). Begin the sample recovery process by
turning the toggle valve on, thus allowing a 6 L/min flow of pure
nitrogen through the purge chamber.
8.3.3 Stop the purge after 30 min. Immediately remove the sorbent
tube(s) from the apparatus and cap both ends. Remove the knockout trap
and transfer the water catch to a 10 mL volumetric flask. Rinse the
trap with organic-free deionized water and transfer the rinse to the
volumetric flask. Dilute to the 10 mL mark with water. Transfer the
water sample to a sample vial and store at 4 deg.C (39.2 deg.F) with
zero headspace. The analysis of the contents of the water knockout trap
is optional for this method. If the target compounds are water soluble,
analysis of the water is recommended; meeting the recovery efficiency
criteria in these cases would be difficult without adding the amount
captured in the knockout trap.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

[[Page 62241]]

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.1........................... Sampling Ensures accurate
equipment leak- measurement of
check. sample volume.
8.2........................... Recovery Ensures accurate
efficiency (RE) sample collection
determination and analysis.
for each
measured
compound..
8.3........................... Calibration of Ensures linear
analytical measurement of
instrument with compounds over the
at least 3 instrument span.
calibration
standards..
------------------------------------------------------------------------

10.0 Calibration and Standardization

10.1 The analytical instrument shall be calibrated with a minimum
of three levels of standards for each compound whose concentrations
bracket the concentration of test compounds from the sorbent tubes.
Liquid calibration standards shall be used for calibration in the
analysis of the solvent extracts. The liquid calibration standards
shall be prepared in the desorption solvent matrix. The calibration
standards may be prepared and injected individually or as a mixture. If
thermal desorption and focusing (onto another sorbent or cryogen
focusing) are used, a certified gaseous mixture or a series of gaseous
standards shall be used for calibration of the instrument. The gaseous
standards shall be focused and analyzed in the same manner as the
samples.
10.2 The analytical system shall be certified free from
contaminants before a calibration is performed (see Section 11.1). The
calibration standards are used to determine the linearity of the
analytical system. Perform an initial calibration and linearity check
by analyzing the three calibration standards for each target compound
in triplicate starting with the lowest level and continuing to the
highest level. If the triplicate analyses do not agree within 5 percent
of their average, additional analyses will be needed until the 5
percent criteria is met. Calculate the response factor (Equation 305-3,
Section 12.4) from the average area counts of the injections for each
concentration level. Average the response factors of the standards for
each compound. The linearity of the detector is acceptable if the
response factor of each compound at a particular concentration is
within 10 percent of the overall mean response factor for that
compound. Analyze daily a mid-level calibration standard in duplicate
and calculate a new response factor. Compare the daily response factor
average to the average response factor calculated for the mid-level
calibration during the initial linearity check; repeat the three-level
calibration procedure if the daily average response factor differs from
the initial linearity check mid-level response factor by more than 10
percent. Otherwise, proceed with the sample analysis.

11.0 Analytical Procedure

11.1 Water Blank Analysis. A water blank shall be analyzed daily
to determine the cleanliness of the purge and recovery system. A water
blank is generated by adding 60 mL of organic-free deionized water to
50 mL of PEG in the purge chamber. Treat the blank as described in
Sections 8.3.2 and 8.3.3. The purpose of the water blank is to insure
that no contaminants exist in the sampling and analytical apparatus
which would interfere with the quantitation of the target compounds. If
contaminants are present, locate the source of contamination, remove
it, and repeat the water blank analysis.
11.2 Sample Analysis. Sample analysis in the context of this
method refers to techniques to remove the target compounds from the
sorbent tubes, separate them using a chromatography technique, and
quantify them with an appropriate detector. Two types of sample
extraction techniques typically used for sorbents include solvent
desorption or direct thermal desorption of test compounds to a
secondary focusing unit (either sorbent or cryogen based). The test
compounds are then typically transferred to a GC system for analysis.
Other analytical systems may be used (e.g., HPLC) in lieu of GC systems
as long as the recovery efficiency criteria of this method are met.
11.2.1 Recover the test compounds from the sorbent tubes that
require solvent desorption by transferring the adsorbent material to a
sample vial containing the desorption solvent. The desorption solvent
shall be the same as the solvent used to prepare calibration standards.
The volume of solvent depends on the amount of adsorbed material to be
desorbed (1.0 mL per 100 mg of adsorbent material) and also on the
amount of test compounds present. Final volume adjustment and or
dilution can be made so that the concentration of test compounds in the
desorption solvent is bracketed by the concentration of the calibration
solutions. Ultrasonicate the desorption solvent for 15 min in an ice
bath. Allow the sample to sit for a period of time so that the
adsorbent material can settle to the bottom of the vial. Transfer the
solvent with a pasteur pipet (minimizing the amount of adsorbent
material taken) to another vial and store at 4 deg.C (39.2 deg.F).
11.2.2 Analyze the desorption solvent or direct thermal desorption
tubes from each sample using the same analytical parameters used for
the calibration standard. Calculate the total weight detected for each
compound (Equation 305-4, Section 12.5). The slope (area/amount) and y-
intercept are calculated from the line bracketed between the two
closest calibration points. Correct the concentration of each waste
sample with the appropriate recovery efficiency factor and the split
flow ratio (if used). The final concentration of each individual test
compound is calculated by dividing the corrected measured weight for
that compound by the weight of the original sample determined in
Section 8.3.1 (Equation 305-5, Section 12.6).
11.2.3 Repeat the analysis for the three samples collected in
Section 8.3. Report the corrected concentration of each of the waste
samples, average waste concentration, and relative standard deviation
(Equation 305-6, Section 12.7).

12.0 Data Analysis and Calculations.

12.1 Nomenclature.

AS = Mean area counts of test compound in standard.
AU = Mean area counts of test compound in sample desorption
solvent.
b = Y-intercept of the line formed between the two closest calibration
standards that bracket the concentration of the sample.
CT = Amount of test compound (g) in calibration
standard.
CF = Correction for adjusting final amount of sample
detected for losses during individual sample runs.
FP = Nitrogen flow through the purge chamber (6 L/min).
FS = Nitrogen split flow directed to the sample recovery
system (use 6 L/min if split flow design was not used).
PPM = Final concentration of test compound in waste sample [g/
g (which is equivalent to parts per million by weight (ppmw))].
RE = Recovery efficiency for adjusting final amount of sample detected
for losses due to inefficient trapping and desorption techniques.

[[Page 62242]]

R.F. = Response factor for test compound, calculated from a calibration
standard.
S = Slope of the line (area counts/CT) formed between two
closest calibration points that bracket the concentration of the
sample.
WC = Weight of test compound expected to be recovered in
spike solution based on theoretical amount (g).
WE = Weight of vial and PEG (g).
WF = Weight of vial, PEG and waste sample (g).
WS = Weight of original waste sample (g).
WT = Corrected weight of test compound measured (g)
in sample.
WX = Weight of test compound measured during analysis of
recovery efficiency spike samples (g).

12.2 Recovery efficiency for determining trapping/desorption
efficiency of individual test compounds in the spike solution, decimal
value.
[GRAPHIC] [TIFF OMITTED] TR17OC00.563

12.3 Weight of waste sample (g).
[GRAPHIC] [TIFF OMITTED] TR17OC00.564

12.4 Response factor for individual test compounds.
[GRAPHIC] [TIFF OMITTED] TR17OC00.565

12.5 Corrected weight of a test compound in the sample, in
g.
[GRAPHIC] [TIFF OMITTED] TR17OC00.566

12.6 Final concentration of a test compound in the sample in ppmw.
[GRAPHIC] [TIFF OMITTED] TR17OC00.567

12.7 Relative standard deviation (RSD) calculation.
[GRAPHIC] [TIFF OMITTED] TR17OC00.568

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References. [Reserved]

[[Continued on page 62243]]

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

[[pp. 62193-62242]] Amendments for Testing and Monitoring Provisions

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