United States Office of Air Quality EPA-450/3-82-002
Environmental Protection Planning and Standards January 1982
Agency Research Triangle Park NC 27711
_
&ERA Revised Test Methods
106 and 107-
Summary of Comments
and Responses
I
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EPA-450/3-82-002
Revised Test Methods 106 And 107-
(Proposed November 18, 1980, 45 FR 76346)
* Summary Of Comments
And Responses
Emission Standards and Engineering Division
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air, Noise, and Radiation
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
January 1982
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This report has been reviewed by the Emission Standards and Engineering Division
of the Office of Air Quality Planning and Standards, EPA, and approved for publication.
Mention of trade names or commercial products is not intended to constitute endorsement
or recommendation for use. Copies of this report are available through the Library
Services Office (MD-35), U. S. Environmental Protection Agency, Research Triangle
Park, N. C. 27711, or from National Technical Information Services, 5285 Port Royal
Road, Springfield, Virginia 22161.
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TABLE OF CONTENTS
Page
Chapter 1. INTRODUCTION 1
Chapter 2. SUMMARY OF CHANGES SINCE PROPOSAL
Chapter 3. SUMMARY OF PUBLIC COMMENTS AND RESPONSES. . 5
Table 1. LIST OF COMMENTERS 19
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CHAPTER 1
INTRODUCTION
On November 18, 1980, the U. S. Environmental Protection
Agency published in the Federal Register (45 FR 76346) revised
Methods 106 and 107, "Determination of Vinyl Chloride from
Stationary Sources," and "Determination of Vinyl Chloride Content
of Inprocess Wastewater Samples, and Vinyl Chloride Content of
Polyvinyl Chloride Resin, Slurry, Wet Cake, and Latex Samples,"
respectively. These revised methods were proposed under the
authority of Sections 112, 114, and 301(a) of the Clean Air Act
as amended.
Public comments were solicited at the time of proposal. The
public comment period was from November 18, 1980, to January 19,
1981, and was extended to February 19, 1981.
Five comment letters were received concerning issues relative
to the proposed test methods. A detailed discussion of these comments
and responses are summarized in this document. The summary of comments
and responses serves as the basis for the revisions which have been
made to the test methods between proposal and promulgation..
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CHAPTER 2
SUMMARY OF CHANGES SINCE PROPOSAL
1. Section 4.1, Method 106. Section 4.1.11 was added to
list tubing fittings and connectors.
2. Section 5.2.3.2(b), Method 106 and Section 7.2.1.2(b),
Method 107. The optional requirement of "...having it analyzed by
the National Bureau of Standards," was changed to "...calibrating
it against vinyl chloride cylinder standard reference materials
(SRM's) prepared by the National Bureau of Standards, if such SRM's
are available."
3. Section 5.2.4, Method 106. The last sentence of this section
was deleted, and the following sentences were added: "Audit cylinders
obtained from a commercial gas manufacturer may be used provided:
(a) the gas manufacturer certifies the audit cylinders as described
in Section 5.2.3.1 and (b) the gas manufacturer obtains an
independent analysis of the audit cylinders to verify his analysis.
Independent analysis is defined here to mean analysis performed by
an individual different than the individual who performs the gas
manufacturer's analysis, while using calibration standards and analysis
equipment different from those used for the gas manufacturer's analysis.
Verification is complete and acceptable when the independent analysis
concentration is within +5 percent of the gas manufacturer's
concentration."
4. Section 6.1, Method 106. The second sentence was revised to
read, "A bag leak check should have been performed previously according
to Section 7.3.2." The fifth sentence was revised to read, "After
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allowing sufficient time to purge the line several times, change the
vacuum line from the container to the bag and evacuate the bag until
the rotameter indicates no flow."
5. Section 6.4, Method 106. The sixth sentence was revised to
read, "Purge the sample loop for 30 seconds at the rate of 100 ml/min,
shut off flow, allow the sample loop pressure to reach atmospheric
pressure as indicated by the H20 manometer, then activate the sample
valve."
6. Section 7.1, Method 106. Reference to Figure 106-2 was
deleted, and Figure 106-2 was deleted.
7. Section 7.2.2, Method 106. The last sentence was revised
to read, "Perform calibration daily, or before and after the analysis
of each emission test set of bag samples, whichever is more frequent."
Two sentences were added that read, "For each group of sample analyses,
use the average of the two calibration curves which bracket that group
to determine the respective sample concentrations. If the two
calibration curves differ by more than 5 percent from their mean value,
then report the final results by both calibration curves."
8. Section 8.2, Method 106. The second sentence was revised to
read, "From the calibration curves described in Section 7.2.2,
determine the average concentration value of vinyl chloride, C , that
corresponds to A , the sample peak area."
9. Section 6.2, Method 107. In Section 6.2.1, the part numbers
were revised to indicate the new, correct numbers.
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10. Section 6.2, Method 107. Section 6.2.4 was added to list
a 100 yl syringe (optional).
11. Section 8.2.1,-Method 107. The fifth sentence was revised
to read, "Obtain the exact sample weight, add 100 ul or about two
equal drops of distilled water, and immediately seal the vial."
12, Section 8.2.4, Method 107. The last sentence was revised
to read, "Prepressurize the vial, and then condition for 1 to 2 hours
as required at 90° C in the analyzer bath."
13. Section 8.3.1.1, Method 107. A sentence was added to
indicate that a clean burr-free needle is mandatory.
14. Section 8.3.1.2(b), Method 107. The dosing line temperature
was changed from 170° C to 150° C.
15. Section 8.3.2, Method 107. Quotation marks were added to
the term "analysis time."
16. Section 9.1, Method 107. Wording was added to optionally
allow the addition of 100 pi of distilled water in place of two drops.
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CHAPTER 3
SUMMARIES OF PUBLIC COMMENTS AND RESPONSES
1. IV-D-1
Summary of Comment: The Agency (EPA) should publish a notice
in the Federal Register to clarify the November 18, 1980 notice on
Test Methods 106 and 107 as to whether the changes in the methods are
proposed or final amendments.
Response to Comment: A notice was published in the Federal
Register on January 6, 1981, Volume 46, No. 3, p. 1318, to clarify
that the changes in Methods 106 and 107 published on November 13, 1980,
were proposed changes.
2. IV-0-2
Summary of Comment: Commenter IV-D-2 requests that Section 5.2.4
of Test Method 106, entitled "Audit Cylinder Standards" further
describe commercial gas manufacturers as an alternative source of
these standards. Section 5.2.4 of Method 106 as proposed November 18,
1980, contains the following statements:
"When available, the tester may obtain audit cylinders by
contacting: Environmental Protection Agency, Environmental
Monitoring Systems Laboratory, Quality Assurance Division
(MD-77), Research Triangle Park, North Carolina 27711. If
Audit cylinders are not available at the Environmental Protection
Agency, the tester must secure an alternative source."
Response to Comment: The last sentence of Section 5.2.4 will be
deleted and several sentences will be added to describe the acceptability
of audit cylinders obtained from commercial gas manufacturers.
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3. IV-D-3
Summary of Comment: Section 7.2.2 of Test Method 106 should be
changed to require calibration at least once every 8 hours of
continuous operation of the gas chromatograph, whereas the method
presently requires daily calibration. If this change would require
too much time to analyze all standards, then at least two of the
standard mixtures could be analyzed every 8 hours. Then the values
generated could be compared to the last complete calibration curve.
If the new values deviate more than 5 percent from the curve, then a
new calibration curve would have to be prepared.
Response to Comment: Section 7.2.2 requires that calibration be
performed daily, or before and after each set of bag samples, whichever
is more frequent. While analysis of a set of Method 106 samples rarely
takes more than 8 hours, it would be an unnecessary burden to
arbitrarily set 8 hours as a cutoff point for valid calibrations. A
sentence will be added, however, to indicate that if calibration
curves deviate by more than 5 percent from their mean, then the results
must be reported by both calibration curves.
4. IV-0-4
Summary of Comment: For Method 106, a leak between the bag inlet
and probe can have a significant effect on the sample. Therefore,
there should be a requirement for leak checking this portion of the
sample system.
Response to Comment: There are no significant pressure drops
when sample is flowing through this portion of the sample train;
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therefore, the requirement to check that all connectors between the
bag and probe are tight should be sufficient.
5. IV-D-4
Summary of Comment:' Add a Section 4.1.11 to Method 106 as follows:
"4.1.11, Fittings and Connectors. All fittings (compression type
or otherwise) used in connecting the sample line from the probe
to the box should be Teflon or stainless steel. Tygon or
surgical rubber tubing may be used to hold two pieces of Teflon
tubing together, provided one tubing end is flush against the
other or fits inside the other."
Response to Comment: This suggested addition may be helpful to
some, and will therefore be added. However, slip connections will not
be suggested as they are prone to leakage.
6. IV-D-4
Summary of Comment: Section 4.3.1 of Method 106 should be revised
to include a combination plotter/integrator, thereby precluding the
problem of sources having to ask if they can be used.
Response to Comment: Section 4.3.8 already describes a strip chart
recorder as optionally equipped with either a disc or electronic
integrator, so no further description should be necessary.
7. IV-D-4
Summary of Comment: In reference to Section 4.3.1, heating the
sample loop should not be mandatory because not all labs will have a
heated valve. It should be sufficient to insulate the valve/loop and
insert a thermometer tip underneath the insulation so that the
temperature is known.
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Response to Comment: A heated sample loop is necessary to prevent
sample intercontamination. A sample valve can be heated by using a
heat tape and rheostat, both of which are readily obtainable.
8. IV-0-4
Summary of Comment: Section 4.3.4 of Method 106 should be
revised to indicate that the regulators used be ones specified by
the gas manufacturer, because it is especially important that proper
regulators be used on calibration gas cylinders.
Response to Comment: No contamination problems resulting from the
interchange of regulators can be foreseen. If only the regulators
specified by the gas manufacturer are required, then unnecessary
expenses may be incurred.
9. IV-D-4
Summary of Comment: Add a Section 4.4.5 to Method 106 as follows:
"4.4.5. Midget Impinger. For use in preparation of vinyl chloride
standards; made of Pyrex glass, with a minimum of grease applied to
the ground glass joint."
Response to Comment: The midget impinger is not required, as
Figure 106-2 is in error. Refer to the response to the comment about
Section 7.1 (See No. 13).
10. IV-D-4
Summary of Comment: Section 6.1 of Method 106 should be revised
to read as follows (changes are underlined):
"Assemble the sample train as shown in Figure 106-1. The bag and
rigid container should have been leak-checked (7.3.2) prior to
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setting up for sample collection. Using a suitable coupler.
connect the vacuum line to the sample line. Place the end of
the probe at the centroid of the stack, and start the pump with
the needle valve adjusted to yield a flow that will fill over
50 percent of the bag volume in the specified sample period.
After allowing sufficient purge time to displace the sample line
volume several times, disconnect the vacuum and sample lines;
then connect the vacuum line to the bag, and evacuate the bag
until the rotameter indicates no flow. (If the bag has been
leak-checked and flow is still indicated, there may be a leak
in the bag-to-guick-connect connection. This should be fixed
before proceeding further.) Start the sample by connecting
the sample line to the bag and the vacuum line to the container.
as illustrated in Figure 106-1. During the sampling period, keep
a constant proportionality between the sample flow rate and stack
flow rate. At all times . . . ."
Response to Comment: The procedure is essentially correct as
proposed. The intent is to prefill the sample bag with some sample,
and then reevacuate the bag while simultaneously making another leak
check. The proposed wording of this section will be slightly changed
to clarify this intent.
11. IV-D-4
Summary of Comment: Section 6.3 of Method 106 needs refinement.
If a pump is used, it should be placed upstream of the rotameter and
downstream of the pressure gauge. Obviously, some vacuum will be
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created in the line. In the case of micro sampling valves (Carle
or Valco) with 1/16-inch tubing connections, the vacuum may be too
high for measurement with a 1-inch water manometer. In using the
option of container pressurization, flow control should be by means
of a needle valve upstream of the sample valve. Otherwise, there is
a possibility of pressurizing the sample loop. Having the water
manometer downstream of the charcoal filter may not result in an
accurate measurement of the absolute sample loop pressure.
Response to Comment: The object of the 1-inch H^O pressure gauge
(not manometer) is to determine that gas in the sample loop has
returned to atmospheric pressure, after sample flow has been stopped.
Container pressurization to move sample gas through the sample loop
should not harm the sample loop.
12. IV-D-4
Summary of Comment: In Section 6.4 of Method 106 as proposed,
the sixth sentence apparently has a phrase missing. It should read
"Purge the sample loop for 30 seconds at the rate of 100 ml/min,
shut off flow, allow the pressure to drop to atmospheric, as indicated
by manometer zero, then activate the sample valve."
Response to Comment: While Section 6.3 already describes this
operation, it may clarify the procedure to repeat it in Section 6.4,
so Section 6.4 will be revised to include this suggestion.
13. IV-D-4
Summary of Comment: Section 7.1 of Method 106, as proposed, makes
reference to Figure 106-2. However, instructions say to inject vinyl
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chloride through the wall of the bag. Figure 106-2 indicates that the
vinyl chloride is to be injected through a septum on the top of the
midget impinger.
Response to Comment: -Figure 106-2 illustrates a standards
preparation procedure not described in the optional standard
preparation section, and therefore Figure 106-2 will be dropped. It
is also felt that the actual standards preparation procedure would not
be enhanced by a figure, so none will be added.
14. IV-D-5
Summary of Comment: The commenter had previously requested and
received approval of an alternative procedure to Test Method 107. The
commenter (IV-D-5) is concerned as to whether or not the promulgation
of a modified Method 107 will mean that approval of his alternative
procedure will be recinded.
Response to Comment: The proposed changes in EPA Method 107 are
meant to enhance the performance of that method, and should not
be interpreted as having any bearing on the prior approval of alternative
test methods.
15. IV-D-5
Summary of Comment: In reference to Section 6.2.1 of Method 107
as proposed, Perkin-Elmer Part No. 105-0118 is no longer a valid part
number for vials, seals, and caps. The correct part numbers are as
follows:
Vials: 0105-0129, Septa: BOO!-0728 (gray butyl rubber septum,
plug style) and 0105-0131 (butyl rubber septa).
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Response to Comment: The commenter is correct, and the revised
part numbers will be included.
16. IV-D-5
Summary of Comment: The proposed procedure of Section 6.3.2 of
Method 107 suggests the use of Porapak Q columns. The commenter has
not been able to get separation of vinyl chloride and acetaldehyde
with the Porapak Q column. The commenter uses two 1.83 meter columns
containing 1 percent Supelco 1000 on Carbopak B, which give adequate
separation of vinyl chloride and acetaldehyde.
Response to Comment: Section 6.3.2 of Method 107, as proposed,
already lists columns for the separation of vinyl chloride and
acetaldehyde. Other columns can also be acceptable, as described in
Section 6.3.2.
17. IV-D-5
Summary of Comment: Section 6.3.10 of Method 107, as proposed,
deals with a proposed addition to this procedure, the head space vial
prepressurizer. The commenter1s analysts indicate that the
prepressurization step was introduced because the authors of Method 107
felt that pressurization just prior to injection, as in the old
procedure, did not allow adequate time for the vapors and the head
space to reach equilibrium. A spot comparison by the commenter shows
no significant difference between the old procedure and the new
prepressurization procedure. In addition, the commenter has had
several problems with leakage once the vials have been prepressurized.
They have found that when butyl rubber septa are used, leaks appear
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through the hole in the septum made by the prepressurization apparatus
after the vial has been pressurized; in addition, when Teflon-faced
septa are used as specified in sampling waste water, they have
experienced great difficulty in sealing the vials so as to preclude
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leaks around the sides of the septa. They have found, however, that
the use of butyl rubber septa is more appropriate in the sampling of
waste water, both from the standpoint of expense and seal ability.
These comments on the prepressurization also apply to paragraphs
8.2, 8.2.3, and 8.2.4 of the proposed Method 107.
Response to Comment: A reference will be added to Section 11,
Bibliography, that explains the need for vial prepressurization.
The Environmental Protection Agency agrees that Teflon septa should
not be used on sample analysis vials. Rather, butyl rubber septa must
be used as specified. Leaks can be greatly reduced by using a clean,
burr-free injection needle, and a statement will be added to that
effect.
18. IV-D-5
Summary of Comment: Section 8.2.1 of the proposed Method 107
requires the two drops of distilled water be added to the contents of
the vial, i.e., resin samples, prior to sealing. The old procedure
required that 100 micro!iters of distilled water must be injected
into the vial after sealing and weighing using a 100 micro!iter
syringe. Although it is just as easy to add two drops of water as it
is to inject 100 microliters of water, most facilities are adapted to
the old procedure and such a change could cause confusion in day-to-day
laboratory operations.
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Response to Comment: Calculations by EPA show that either
100 yl or two drops of water will saturate the sample analysis vial,
so the method will be changed to indicate that either amount is
satisfactory.
19. IV-D-5
Summary of Comment: Section 8.2.2 of Method 107, as proposed,
specifies a dewatering procedure which is different from that in the
old procedure. The commenter's alternative method is based upon the
idea that an accurate weight of the dewatered resin be obtained, and
further that the sample must be weighed to a specified weight to
provide for ease in calculation. In this respect, the resulting wet
cake, when dewatered by the proposed procedure, is much wetter than
that in the old procedure, which makes accurate weighing to a specified
weight virtually impossible. Therefore, it is suggested that the old
dewatering procedure, i.e., that which is employed in existing Method
107, be retained in favor of the proposed dewatering procedure.
Response to Comment: The dewatering procedure was changed due to
a concern that in vacuum filtering a sample, vinyl chloride might be
removed from the sample wet cake. The Agency does not, however, have
reason to disallow the old procedure as long as some control is
exercised to keep the vacuum filtering of each sample to a minimum.
Since in the revised procedure, all samples are weighed after placing
in the sample analysis vial, no difficulty should be experienced with
the requirement to weigh to a constant weight.
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20. IV-D-5
Summary of Comment: Section 8.2.4 of the proposed Method 107
specifies a 2-hour conditioning time. Comparisons the commenter has
made show that a 1-hour conditioning time gives the same result as a
2-hour conditioning time. Therefore, it is suggested that the
procedure for a 1-hour conditioning time be retained.
Response to Comment: The change to 2-hours for sample conditioning
was made as a result of a revised industry procedure. However, as
1 hour may be sufficient, EPA will change the procedure to allow a
shorter conditioning time.
21. IV-D-5
Summary of Comment: Section 8.3.1.2 of the proposed Method 107
specifies a 170° C temperature for the dosing line. However, the
F42 and F45 model chromatographs, do not provide for a temperature
setting of 170°. These models only provide for selection of
temperatures of 50, 100, 150, 200, and 250°. Table 1 shows a
comparison of temperatures specified by the proposed procedure, by
the old procedure, and the temperatures that the commenter uses both
with an F42 and an F45 unit.
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TABLE 1
Analysis (Temperature)
Revised
Old
Commenter's
Oven
Dosing Line
Injection block
140° C
170° C
170° C
50° C
140° C
140° C
F42
105
150
170
F45
105
150
170
The commenter believes that a temperature setting of 150° C
should be specified for the dosing line.
Response to Comment: The commenter is correct as to the available
temperature settings, so a change will be made to specify a temperature
of 150° C for the dosing line.
22. IV-D-5
Summary of Comment: Section 8.3.2.b of the proposed Method 107
states, in programming the chromatograph analysis time, that "the normal
setting is approximately 70 percent of the VCM retention time." This is
a misstatement. The correct statement should be "VCM retention time is
normally 70 percent of the analysis time." Table 2 sets forth the
typical values the commenter has obtained using the F42 and F45 models.
Response to Comment: The commenter is correct in that the term
"analysis time" as used in Section 8.3.2.b is a misnomer. The term is
used to signal when backflushing is to occur, and the specified setting
is correct. Quotation marks will be placed around the term to alleviate
any further confusion.
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TABLE 2
Retention and Analysis Time
F42 F45
V.C. retention 2.2
Analysis time 3.4
Analysis time
(V.C. RT/.70) 3.1
2.4
3.8
3.4
23. IV-D-5
Summary of Comment: In reference to Section 9.1 of the proposed
Method 107, the commenter questions adding two drops of water prior to
sealing the vial as opposed to injection of 100 micro!iters of water
after sealing. Table 3 provided by the commenter shows responses
for two trials on a 52 ppm VC standard comparing the addition of two
drops of water vs. the injection of 100 microliters of water. These
results show both a reduced and a more variable response when two
drops of water are added as opposed to injection of 100 microliters.
Therefore, the commenter suggests that in this paragraph, in addition
to Section 8.2.1, that the method specify the injection of 100
microliters of distilled water after sealing of the vial.
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TABLE 3. INTEGRATOR RESPONSE FOR 52 PPM VC STD
Trial 1
2 Drops
water
13100
14049
13578
Avg. 13576
SD 474
Injection .
100 yl
14724
14595
14353
14558
190
Trial 2
2 Drops
water
12648
11997
Avg. 12322
SD 460
Injection
100 ul
13621
13874
14216
14558
299
Response to Comment: A change will be made to allow either
100 yl or 2 drops of water. Refer to the response to the comment
about Section 8.2.1.
24. IV-0-5
Summary of Comment: In reference to Section 9.2 of the proposed
Method 107, the commenter feels that the proposed requirement that
a straight line be drawn through the calibration points as derived
by the Least Squares Method is an improvement over the old procedure.
Response to Comment: No response is required.
25. IV-0-5
«,
Summary of Comment: In reference to Section 10.1 of the proposed
Method 107, the commenter feels that the use of the calibration curve
as proposed is an improvement over the old procedure.
Response to Comment: No response is required.
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TABLE 1. LIST OF COMMENTERS
Docket No. A-80-50
Docket item No. Commenter/Affi1iation
IV-D-1 Scott W. Bowen, Associate, Beveridge,
Fairbanks and Diamond
1333 New Hampshire Avenue, N.W.
Washington, D.C. 20036
IV-D-2 Robert E. Squires, Operations Manager
Scott Specialty Gases Division
Scott Environmental Technology, Inc.
Plumsteadville, Pa. 18949
IV-D-3 G. Vinson Hellwig, Senior Environmental
Engineer
PEDCo Environmental, Inc.
Suite 503
505 South Duke Street
Durham, N.C. 27701
IV-D-4 Robert E. James, Ph.D., Senior Scientist
Engineering-Science
3109 North Interregional
Austin, Texas 78722
IV-D-5 Thomas V. Malorzo, Senior Regulations
Analyst
717 North Harwood Street
Dallas, Texas 75201
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing;
1. REPORT NO.
EPA 450/3-82-002
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Revised Test Methods 106 and 107 - (Proposed November
18, 1980, 45 FR 76346) Summary of Comments and
Responses
5. REPORT DATE
January 1982
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO
Emission Standards and Engineering Division
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Emission Measurement Branch (MD-19)
Emission Standards and Engineering Division
U. S. Environmental Protection Agency
Research Triangle Park, N. C. 27711
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
DAA for Air Quality Planning and Standards (MD-10)
Office of Air, Noise, and Radiation
U. S. Environmental Protection Agency
Research Triangle Park, N. C. 27711
13. TYPE OF REPORT AND PERIOD COVERS.
14. SPONSORING AGENCY CODE
EPA/200/04
15. SUPPLEMENTARY NOTES
16. ABSTRACT ~ ~~ —
This document addresses the public comments submitted after proposal of
the vinyl chloride methods in the Federal Register. Changes made to the methods
as a result of these comments are included. This document serves as the basis
for the revisions which have been made to the test methods between proposal and
promulgation.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATl Field/Group
13 B
8. DISTRIBUTION STATEMENT
Release Unlimited
19. SECURITY CLASS (Tins Report/
Unclassified
21 NO OF PAGES
23
Unclassified
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