EPA-560/4-74-001
App.
PRELIMINARY ASSESSMENT
OF THE ENVIRONMENTAL PROBLEMS
i
ASSOCIATED WITH
VINYL CHLORIDE AND
POLYVINYL CHLORIDE
(Appendices)
Report on the Activities and
Findings of the Vinyl Chloride Task Force
ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C.
SEPTEMBER 1974
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PRELIMINARY ASSESSMENT OF THE ENVIRONMENTAL PROBLEMS
i
ASSOCIATED WITH
VINYL CHLORIDE AND POLYVINYL CHLORIDE
(Appendices)
Report on the Activities and Findings of the
Vinyl Chloride Task Force
Environmental Protection Agency
Washington, DC
September 1974
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TABLE OF CONTENTS
APPENDICES
I. Selected Economic Considerations 1
Production Levels 1
Competitive Substitution 1
International Aspects 4
Control Technology 4
II. Producers of Vinyl Chloride and Polyvinyl Chloride 6
IT VC ^Producers 6
^ PVC Producers 6
PVC Copolymer Producers 8
1C
>v III. The Materials Balance at Vinyl Chloride and 10
t\. Polyvinyl Chloride Facilities
V.
(-o Vinyl Chloride Production Facilities 10
£? Polyvinyl Chloride Polymerization Facilities 11
(<)
IV. Interim Method for Sampling and Analysis of Vinyl 17
Chloride in Waste Water Effluents and Air
Emissions
Scope and Application 17
Summary of Analytical Procedures 17
Inte rf e r enc e s 17
Apparatus and Materials 18
Reagents, Solvents, and Standards 19
Sampling 20
Calibration 23
Procedure 25
Quality Control 25
V. Summary of Regional Activities 26
Region I: Leominster, Massachusetts 26
Region II: Flemington, New Jersey 27
Region III: Delaware City, Delaware 27
S. Charleston, W. Virginia
Region IV: Louisville, Kentucky 28
Region V: Painesville, Ohio 28
Region VI: Plaquemine, Louisiana 29
Region IK: Long Beach, California 29
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VI. Persistence of Vinyl Chloride 31
Behavior of Vinyl Chloride in Air 31
Behavior of Vinyl Chloride in Water 31
Behavior of Vinyl Chloride in Closed Rooms
VII. Health Effects of Vinyl Chloride 32
Occupational Cases of Liver Angiosarcoma 34
Cases of Hepatic Angiosarcoma, Connecticut, 38
1935-1973
Observed Deaths/Expected Deaths in VC 40
Workers
Summary of Toxicological and Epidemiological 44
Studies on Vinyl Chloride
VIII. Disposal of Products Containing Polyvinyl Chloride 63
Incineration 63
Landfilling 64
Resource Recovery 65
DC. Activities of Task Force 67
ii
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APPENDIX I
SELECTED ECONOMIC CONSIDERATIONS
Production Levels
During 1973, VC production was at the 5. 3 billion pound level
with PVC and its copolymers at the 4.6 billion pound level. PVC
has become a very important polymer as evidenced by the broad
dependence of nearly every branch of industrial and commercial
activity upon products and components fabricated from this plastic.
In Table 1, major PVC products manufactured during 1973 are iden-
tified.
The U. S. VC/PVC industry has been operating for more than
forty years, and over the past five years has shown an average annual
growth rate of 14 percent - - a rate of growth that had been expected
to taper off only moderately in the next few years.
The size of this industry can be appreciated by considering that
the synthesis of the monomer is conducted in fifteen U. S. plants, and
forty-three facilities are engaged in polymerization of PVC (including
its use as a copolymer) with almost all of these plants currently
operating at or near capacity. At least 7,500 plants are engaged in
fabricating products from PVC. About 1,500 workers are employed
in monomer synthesis and an additional 5,000 in polymerization
operations. Estimates have suggested that up to 350,000 workers
may be associated with the fabrication plants.
The wholesale value of the annual output of fabricated products
based on PVC is at least several billion dollars.
Competitive Substitution -r .
Should requirements for worker safety or environmental controls
drive the price of PVC resin upward, it seems likely that some PVC
products would be displaced by products using other plastics or other
materials. Other products dependent on PVC might disappear alto-
gether from the marketplace. Probably one-fourth to one-third of
current PVC products by value are marginally competitive with other
plastic products. At significantly higher prices a lesser number
probably would find substitutes in other materials at higher costs.
Identified in Table 2 are a few of the substitute materials that might
be considered. For some uses, there are no apparent substitutes.
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Table 1
MAJOR PVC PRODUCTS
Market Category
I. Apparel
II. Building and
Construction
III. Electrical
IV. Home
V. Packaging
VI. Recreation
VII. Transportation
VIII. Miscellaneous
Products
Baby pants
Footwear
Outerwear
Extruded foam moldings
Flooring
Lighting
Panels and siding
Pipe and conduit
Pipe fittings
Rainwater systems, soffits,
facias
Swimming pool liners
Weatherstripping
Windows
Wire and cable
Appliances
Furniture
Garden hose
Housewares
Wall coverings and wood
surfacing films
Blow molded bottles
Closure liners and gaskets
Coatings
Film
Sheet
Phonograph records
Sporting goods
Toys
Auto mats
Auto tops
Upholstery and seat covers
Agriculture (incl. pipe)
Credit cards
Laminates
Medical tubing
Novelties
Stationery supplies
Tools and hardware
Other
1973
1000 metric tons
12
66
31
26
211
5
39
525
44
16
18
16
26
194
20
145
18
51
54
36
9
9
59
35
66
25
88
18
15
83
66
8
23
23
7
18
8
45
Total
2158
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Table 2
SUBSTITUTE MATERIALS FOR PVC PRODUCTS
PVC PRODUCT
Pipe & Tubing
Flooring
Electrical Insulation
Records
Film & Sheet Products
Coatings
Household Goods
Packaging
SUBSTITUTES
Polyethylene
Polypropylene
Metals
ABS resins
Asphalt
Wood
ABS resins
Polyethylene
Polyp r opy 1 ene
EPDM rubbers
SBR rubbers
TFE plastics
ABS resins
Acrylics
Polyvinylidene chloride
Polyethylene
Polypropylene
Cellulosics
Acrylics
Polyurethanes
Cellulosics
Styrene
Polyethylene
Polypropylene
Wood
Metals
Acrylics
Polyethylene
Polypropylene
Polyvinylidene chloride
Cellulosics
Acrylics
Polyurethanes
Glass
SAME
PRICE RANGE
X
X
X
X
X
X
X
X
X
X
X
X
HIGHER PRICE
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
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International Aspects
U. S. based manufacturers currently produce about one-third of the
western world1 s supply of resins, with the U. S. market also consuming
about one-third of the total. In 1973, 3.7 percent of PVC and 7.{} percent
of VC manufactured in the United States were exported. Prior to the
recent U. S. concern over worker and environmental controls at VC and
PVC facilities, there was no reason to anticipate a major change in the
U. S. share of production or market during the next few years. Recent-
increases in demand for PVC resins -- and concurrently for VC --at
attractive prices have been of worldwide dimensions with expansion plans
for PVC manufacturing being considered by a number of companies at-
home and abroad.
There is presently an import duty on PVC resin from countries with
status as Most Favored Nations of 1 1/4 cents per pound plus six percent
ad valorem and from other nations of four cents per pound plus 30 per-
cent ad valorem. Given the current U. S. market price of 18 to 24 cents
per pound for the general purpose uncompounded resin, there has been
little incentive to import PVC resin. Also, there currently is little
export incentive because of short U. S. supply and unattractive foreign
prices. However, higher prices as a result of more stringent worker
or environmental controls in PVC resin plants in the United States than
abroad might well stimulate significantly increased imports.
Control Technology
While there appear to be a number of general approaches for reducing
the discharge of VC into the environment at VC and PVC resin plants
and the discharge of PVC at resin plants, in many respects the approaches
must be tailored to the individual plants. All VC plants and some PVC
resin plants are outdoors while other PVC plants are at least partially
enclosed. A variety of production processes are used, and different
kinds of technology are employed. However, there are some common
measures that would reduce VC emissions.
FOR VC PLANTS:
1. Reducing the escape into the atmosphere of VC when venting the tank
car gauge tube, disconnecting the feeding line, and closing the
valves during rail tank car loading. Mechanical disconnect de-
vices and double block and bleed piping are available to ease this
problem.
2. Improving the quality of pumps to reduce the possibility of leakage
due to failure of seals. Pumps are available today which could
minimize this problem.
3. Venting unintentional leaks and spills into a system which is flared
and, preferably, scrubbed.
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FOR PVC RESIN PLANTS:
1. Collection and destruction of purge gases from the reaction kettles
prior to opening for cleaning, sampling, or recharging.
2. Centralized collection and filtering of VC vapor discharges from
dryers and centrifuges.
With regard to PVC particulate in air and water discharges, improved
housekeeping and relatively simple ventilation filtering systems are usu-
ally technically feasible and effective.
Laboratory data have shown that VC can be adsorbed on activated
carbon. Concentrated VC vapor streams have produced a recovery work-
ing capacity on carbon equivalent to about ten percent of the carbon weight.
Ambient air contaminated with low levels of VC produces significantly
lower adsorbent working capacities. Control of dilute VC is therefore
possible but may not be practical using activated carbon. Carbon regene-
ration using steam or pressure swing appears possible, with recovery
of desorbed VC for recycle.
Clearly, these approaches will not eliminate losses but should mate-
rially reduce them. In the longer run, the development of continuous
flow processes, the use of larger kettles, better housekeeping, and/or
reductions in the number of feed lines might result in more dramatic
reductions of VC leakage.
REFERENCES
1. Modern Plastics, Jan 1974, p. 43
2. The 1972 Census of Manufacturers shows 7,574 plants manufacturing
miscellaneous plastics products (SIC 3079), a substantial number of
which use PVC. SIC 3079 probably covers most, but not all, PVC
fabricators.
3. Discussions with representatives of the Department of Commerce,
Manufacturing Chemists Association, and Society of Plastics Industry.
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APPENDIX; I
PRODUCERS OF VINYL CHLORIDE AND POLYVINYL CHLORIDE
The major producers of VC, PVC, and PVC copolymers are listed in this
section with the plant location and available capacity data.
VC Producers
Locatibn
Annual Capacity
(Millions of Pound,
Allied Chemical Corporation
X
American Chemical Corporation
Continental Oil Company
Dow Chemical, U.S.A.
Ethyl Corporation
B. F. Goodrich Chemical Company
Monochem, Inc.
PPG Industries, Inc.
Shell Chemical Company
Tenneco, Inc.
Baton Rouge, La.
Long Beach, Calif.
Westlake, La.
Freeport, Tex.
Oyster Creek, Tex.
Plaquemine, La.
Baton Rouge, La.
Pasadena, Tex.
Calvert City, Ky.
Geismar, La.
Lake Charles, La.
Guayanilla, P. R.
Deer Park, Tex.
Norco, Tex.
Houston, Tex.
300
175
650
200
700
390
300
150
1000
300
400
500
840
700
225
PVC Producers
Air Products and Chemicals, Inc.
American Chemical Corporation
Borden, Inc.
Continental Oil Company
Calvert City, Ky.
Pensacola, Fla.
Long Beach, Calif.
niiopolis, ELI.
Leominster, Mass.
Aberdeen, Miss.
Oklahoma City, Okla.
150
50
150
140
180
285
240
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Company
Diamond Shamrock Chemical Company
Ethyl Corporation
The Firestone Tire & Rubber Company
The General Tire & Rubber Company
B. F. Goodrich Chemical Company
Locations
Deer Park, Tex.
Delaware City, Del.
Baton Rouge, La.
Annual Capacity
(Millions of Pounds)
270
100
180
The Goodyear Tire & Rubber Company
Great American Chemical Corporation
Hooker Chemical Corporation
Keysor-Century Corporation
Monsanto Company
National Starch & Chemical Corporation
Olin Corporation
The Pantasote Co. of New York, Inc.
Robintech, Inc.
Stauffer Chemical Company
Tenneco Chemicals, Inc.
Union Carbide Corporation
Perryville, Md. 230
Pottstown, Pa. 270
Ashtabula, Ohio 125
Pleasants County, W. Va. 50
Avon Lake, Ohio 140
Henry, HI. 140
Long Beach, Calif. 140
Louisville, Ky. 340
Pedricktown, N.J. 170
Niagara Falls, N. Y. 100
Plaquemine, La. 100
Fitchburg, Mass. 40
Burlington, N.J. 180
Hicksville, N. Y. 15
Saugus, Calif. 35
Delaware City, Del. 35
Springfield, Mass. 70
Meredosia, HI. 10
Assonet, Mass. 150
Passiac, N.J. 60
Point Pleasant, W.Va. 90
Paine sville, Ohio 250
Delaware City, Del. , 175
Burlington, N.J. 165
Flemington, N.J. 70
South Charleston, W. Va. 160
Texas City, Tex. 240
Uniroyal, Inc.
Paine sville, Ohio
140
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PVC Copolymer Producers
Company Locations
A. Polyvinyl Chloride-Propylene Copolymer Resins
Air Products and Chemicals, Inc. Calvert City, Ky.
B. Polyvinyl Chloride-Vinyl Acetate Copolymer Resins
Air Products and Chemicals, Inc. Calvert City, Ky.
American Chemical Corporation Long Beach, Calif.
Atlantic Tubing & Rubber Company Cranston, R. I.
Borden, Inc. Bainbridge, N. Y.
Compton, Calif.
Demopolis, Ala.
Illiopolis, D.1.
Leominster, Mass.
The Firestone Tire & Rubber Comany Pottstown, Pa.
B.F. Goodrich Chemical Company Avon Lake, Ohio
Louisville, Ky.
Hooker Chemical Corporation Hicksville, N.Y.
Keysor-Century Corporation Saugus, Calif.
National Starch and Chemical Corporation Meredosia, 111.
Olin Corporation Assonet, Mass.
The Pantasote Company of New York, Inc. Passaic, N. J.
Point Pleasant, W. Va.
C. Polyvinyl Chloride-Vinylidene Chloride Copolymer Resins
BASF Wyandotte Corporation South Kearny, N.J.
Borden, Inc. Bainbridge, N.Y.
Compton, Calif.
Demopolis, Ala.
Hliopolis, 111.
Leominster, Mass.
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Dow Chemical, U.S.A. Midland, Mich.
B.F. Goodrich Chemical Company Louisville, Ky.
W. R. Grace & Company Owensboro, Ky.
South Acton, Mass.
Morton-Norwich Products, Inc. Ringwood, El.
National Starch and Chemical Corporation Meredosia, 111.
SCM Corporation Huron, Ohio
Tenneco, Inc. Burlington, N. J.
Flemington, N. J.
Union Carbide Corporation Institute and South
Charleston, W.Va.
Texas City, Texas
REFERENCES
1. 1974 Directory of Chemical Producers, USA, Chemical Information Ser-
vices, Stanford Research Institute, Menlo Park, California, 1974.
2. Chemical Marketing Reporter, May 20, 1974.
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APPENDIX III
THE MATERIALS BALANCE AT VINYL CHLORIDE" AND
POLYVINYL CHLORIDE FACILITIES
Vinyl Chloride Production Facilities
Detailed, reliable data for estimating material losses at VC facilities
with precision are not readily available. Therefore, only generalized
estimates have been attempted.
A simplified block diagram for production of VC from ethylene and
chlorine is shown in Figure 1. Some VC complexes utilize oxychlorination
units; others produce ethyl chloride from the by-product hydrogen chloride
(HC1) and ethylene. However, the production of dichloroethane (EDC)
allows for many approaches to recycling of light and heavy materials such
that the losses of VC -are reduced. Even vent streams of inerts can be
scrubbed with EDC for maximum removal of VC before venting. Light
ends such as methane are usually flared and VC is converted to water
and small amounts of HC1.
VC losses have come primarily from vent streams, the storage and
transportation loading systems, and seepages from pumps. If vent streams
are not scrubbed or flared, the amount of VC reaching the atmosphere
increases considerably. This in turn is influenced by the purity of the
ethylene and the chlorine being fed into the units. Usually, these inerts
come out in the EDC unit but may be carried on depending upon the pro-
ducer's philosophy regardingthe purity of the EDC to be fed to the cracker.
Experience has been that the higher the purity of EDC both with regard
to light and heavy material, the greater the efficiency of the cracking.
It is frequently difficult to pinpoint the areas and quantities of VC
losses. However, some generalizations can be made for, as an example,
a plant producing 500 million pounds per year of VC. (The industry
is heading toward plants of this size and larger.) Tank car loading
losses may be several hundred pounds per day. Vent stream losses
could reach another 100 pounds per day while losses of VC entrapped
in the water effluent might be a few pounds per day. In addition to these
very small operating losses, there are undoubtedly unintentional losses
from leaking pumps, flanges, and containment vessels, with total plant
losses probably less than 0.1% or less than 500,000 pounds per year.
From an environmental standpoint, the disposal of the heavy chlori-
nated hydrocarbons may also present a problem. Some are sold to solvent
scrap dealers for salvage. In the past much of the material has been
dumped at sea or put into landfills or deep wells. More recently, incin-
eration has been used, which is known to produce HC1 emissions.
10
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Polyvinyl Chloride Polymerization Facilities
Reasonably reliable data are available for estimating material losses
at PVC facilities. However, generalizations applicable to the entire
industry must be surrounded with many caveats. It must be emphasized
that there are a number of PVC processes, and each plant has its own
idiosyncrasies.
VC losses will fluctuate depending on the care exercised in operating
the PVC plant, types of products produced, frequency of product change,
method of PVC shipment, and emergency situations. Estimates of losses
have varied widely in the industry, indicating the complexity of establish-
ing precise losses for a given facility and overall losses on a nationwide
basis.
In general, older PVC plants are smaller than those being built today
and are equipped with smaller sized reactors. With small reactors, thr
number of batches required to produce a given amount of PVC is greater-,
and thus the number of process steps are increased with a greater poten-
tial for loss of both VC and PVC. Further, a small plant has the disadvan -
tage of having to make frequent resin changes to meet customer demands.
During these changeovers a certain amount of off-grade resin is produced.
In addition, older plants have the added burden of higher maintenance
than new plants, but this tends to stabilize after a few years. The handl-
ing of VC and the production of the high quality resins which are demanded
by the marketplace require a reasonable maintenance program. Mainte-
nance consists primarily of the care of agitator seals, pump seals, and
valves and the removal of polymer which slowly builds up in VC lines --
primarily in the recovery system. Although many older facilities have
been in operation for years, they are usually not the same as when first
installed. Some of the operators have continually updated the plants for
many reasons including labor savings systems, new product require-
ments, replacement of wornout equipment, addition of new product lines,
and safety.
When VC was cheap and there was little concern about its toxicity,
the emphasis was almost exclusively on productivity. Often this resulted
in high losses of VC to the environment as recovery cycles were reduced.
Today, the picture is changing. Not only are the producers trying to
reduce the direct VC losses, but they are also trying to minimize PVC
losses by scheduling longer production runs between product changes.
As an example, the newer large plants are setup with multiple production
lines. This allows the dedication of one line to a given product which
results in very low resin loss due to product change.
11
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The traditional method of stating yield of VC in PVC plants has
been based upon pounds of prime resin in the bag as compared to VC"
invoiced. This often has led to a misunderstanding about VC losses
with the interpretation that a 94% yield means 6% VC loss to the envi-
ronment. In fact some VC may never actually be received because of
the inability to measure the weight of tank cars accurately, some of the
losses are in the form of PVC scrap, and some losses escape as PVC
particles.
A properly run and maintained suspension plant using technology that
is ten years old should be capable of obtaining a 95% or higher yield
unless some especially esoteric resin is being produced along with large
amounts of scrap or off-grade resin. For the older plants, the losses
will probably be significantly higher. Other than overall sloppy operation,
the recovery system is the single most important part of the plant govern-
ing VC losses. If insufficient time is allowed or vacuum is not applied,
then the VC content in the PVC/water slurry will be greater than neces-
sary. As a result, VC losses will occur in the centrifuge effluent water,
drier/ product collector vent air, the venting of the reactor, and the slurry
tank.
The magnitude of VC and PVC losses in a typical PVC plant is
described in Figure 2. These losses are expressed as a range of losses
depending on the feed rate, reactor size, reactor cleaning procedures,
batch sizes, level of technology, and general housekeeping and operating
procedures.
The following comments on manufacturing practices may help put
these losses into perspective:
1. VC Feed - This is shipped as virtually 100% VC and does not
normally contain an inhibitor.
2. VC Unloading - Considering normal losses in disconnecting the
piping, sampling, tank gauging, pump and compressor seals to the tank
cars, losses to the atmosphere should not be greater than 100 pounds
per car.
3. VC Charging - A 0.05% loss between storage and polymerization
should cover losses from flanges and seals throughout all VC handling
equipment.
4. Polymerization - The loss from build-up of PVC on the walls of
the reactor is split between reactor wash-out and the slurry strainer.
5. Reactor Venting - Before the reactor can be cleaned, residual VC
is venteinAfter recovery and emptying the PVC resin, the reactor is
full of a mixture of air, moisture, and VC at ambient conditions.
12
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6. Recovery - Processing schemes will vary, but one of the most
widely used is the direct recovery of unreacted VC from the reactor.
While the reaction can be carried out further, economically it is essen-
tially complete at 90% conversion or even less depending on the type of
resin. At this point the residual VC is recovered by means of compres-
sors which evacuate VC from the reactor. The recovered VC is con-
densed and distilled before recycling to the reactor.
7. Drying - Unreacted VC is collected in the recovery system but
there are losses of polymer in the drier due to coalescence of the resin
and periodic clean-out. This is almost entirely scrap.
8. Product Collector - Most plants use bag collectors so that the loss
of resin is less than one pound per hour, but there are losses due to
product changes which raise the total.
X
9. Screening - Oversize resin is removed from the final product.
This material consists of scrap and off-grade resin. With the current
PVC shortage much of this off-grade resin is used as prime resin by
special customers.
10. Miscellaneous - In addition to the above losses, others occur as
scrap or off-grade polymer and as quality control samples.
a. Bad Batches - Most plants experience batches which are off
specification. These range from "just slightly off" to solid
batches, with losses at 2 to 3 batches per month or about 0.4%
or 40 pounds per hour average. . Salvage value depends upon
the degree of ' off-grade" and market conditions.
b. Samples - Probably about 0.05% or 5 pounds per hour and is
usually destroyed in testing.
c. Polymer Build-up - VC slowly polymerizes in the pipe lines,
particularly the recovery system, and must be removed peri-
odically. No quantitative value is available for this loss.
d. Spillage - Some of the product is shipped in bulk and some
is bagged. While some spillage occurs in bulk handling, more
occurs in bag filling and in bag breakage.
e. Centrifuge Effluent - Some PVC enters the effluent water.
11. Product Change-Over -As indicated previously there are losses in
the drier and collector due to cleaning for changes from one product to
another. In addition one must segregate the first product that comes
through this system. - The amount can vary widely depending upon the
number of changes and the sensitivity of the product to contamination from
the previous product.
13
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The foregoing analysis, together with estimates provided by industry,
suggests that the losses of VC at PVC polymerization facilities currently
range from about 3.0 to 6.3% while PVC losses are on the order of 1. 3%.
14
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APPENDIX IV
INTERIM METHOD FOR SAMPLING AND ANALYSIS OF VINYL
CHLORIDE IN WASTE WATER EFFLUENTS AND AIR EMISSIONS
Scope and Application
The initial basis for this method was developed during the moni-
toring program carried out by EPA Region IV in March and
April. The techniques used by Region IV provided guidance for
the monitoring activities of other Regions, and the experiences
of all Regions were then incorporated into this refined versicn of
the original Region IV approach.
This method is applicable to VC determinations in water effluents,
sludges and scums, and atmospheric emissions. The limit of
detection is approximately 0.06mg/l in water and 0.06 ppm (v/v)
in air samples.
Summary of Analytical Procedures
Water composite samples, air continuous composite bag samples,
and air and water grab samples are analyzed without cleanup by
gas chromatography (GC). Separations are effected by selection
of one of two types of columns depending upon the nature of the
sample. Detection is by means of the flame ionization detector
(FID). Tetrahydrofuran extracts of sludges and scums are used
for injection into the GC. Air continuous samples on activated
carbon are extracted with carbon disulfide, and the extract is
analyzed by direct injection into the GC.
Calibration curves are developed using gravimetrically prepared
calibration solutions, or by using known dilutions of VC in carrier
gas.
VC confirmation should be made by mass spectrometric analysis
of the GC eluent if possible. Independent confirmation may also
be made in the event of extraordinarily high VC concentration sam-
ples by using long path Fourier transform IR spectrophotometry.
This IR technique requires special equipment and about 20 cubic
feet of air samples.
Interferences
Certain volatile hydrocarbons such as neopentane, butadiene, and
freon 12 have elution characteristics similar to VC. However, on
the GC column substrates specified in these procedures, these
have not usually presented problems of resolution of the VC peak.
When column substrates other than those specified have been used,
impurities from solvents and carbon adsorbents have been
17
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found to interfere with the VC elution peak. Under certain condi-
tions a peak is associated with the injection and subsequent with-
drawal of the microsyringe into and from the GC septum. These
peaks can also give interferences with the VC peak. Withdrawal
should be timed to avoid overlap of this peak with the VC peak.
Apparatus and Materials
Gas Chromatograph
Flame lonization Detector
Recorder - any potentiometric strip chart recorder which is
compatible with the detector system. An integrator is also
desirable to estimate peak areas.
Column Materials for Waste Water, Sludge, or Scum Samples
Borosilicate glass tube or stainless steel tube - 6' x 2. 5
mm ID preferred. When GC configuration requires columns
of other dimensions, these should be used.
Solid support - 60 to 80 mesh Gas Chrom Q
Liquid Phase - 4% FFAP on specified solid support (weight
percent). Liquid phase on solid support can be purchased
directly from commercial distributors.
Column Materials for Air Samples
Borosilicate glass tubing or stainless steel tubing - 8' x 2.5
mm ID preferred. When GC configuration requires columns
of other dimensions, these should be used.
Solid support - Carbopak A
Liquid phase - 0.4% Carbowax 1500 on solid support (weight
percent). Liquid support on solid phase can be purchased
9 directly from commercial distributors.
Continuous Air Monitoring Materials - Carbon Adsorption Option
&
w Adsorption Tube - pyrex glass, 18" x 3/8" OD
Activated coconut charcoal, 8-16 mesh. Any good commer-
* cial grade, e.g. Fischer Scientific Company can be used.
- Becton-Dickson27 gage 3/8" hypodermic needle flow control
Vacuum pump
Air flow meter
18
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Continuous Air Monitoring Materials and Equipment - Bag Sampling
Option
Environmental Measurements, Inc., Programmable Bag Sampler
Tedlar bags (or equivalent)
Gas Pressure Regulator (0-5 PSIG)
Microsyringes - 10, 25, 50, and 100 microliter (graduated)
Gas-tight sample syringes - 1 and 50 ml (graduated)
Vacuum Sampling Cans - 370 ml steel Vacu-Samplers, or glass
sampling bottles. Cans and bottles should be flushed with clean
air or nitrogen and evacuated prior to use. Evacuated containers
should be protected from rough handling to prevent implosion or
collapse.
Sampling Bags (Tedlar or equivalent) - 12" x 12", 36" x 36",
equipped with sampling valves and speta for GC sample withdrawal
Automatic water sampler - compositor (manual sampling is
optional) equipped with sample refrigeration capabilities, and a
a means to prevent loss of vinyl chloride from open bottles
Glass sampling bottles with teflon lined screw type caps - 50 ml
capacity or other sizes depending upon sampler requirements
Septum-sealed vials - 1 to 10 ml capacity
Volumetric Flask, Glass stoppered, 25 ml
Medicine droppers
Dedicated GC/M. S» for confirmatory tests (preferable)
Barometer
The rmo me te r
Anemometer
Reagents, Solvents, and Standards
Carrier gases - zero nitrogen or helium
FID gases - zero hydrogen, oxygen
Tetrahydrofuran, reagent grade,, peroxide-free
19
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Carbon tetrachloride (reagent grade)
Carbon disulfide (reagent grade)
Standards
VC in zero air, 50 ppm (+ 2%) v/v
VC, analyzed reagent grade (lecture bottle)
Sampling
A. Water Samples
All waste water discharge points identified in NPDES permits
should be sampled for VC. A minimum of three successive
24-hour composite samples of each site should betaken. Com-
positing interval should be one hour (manual or automatic
sampling is optional). Compositing interval of 20 minutes may
be used if the automatic sampler has this capability. Samples
should be taken at waste treatment units such as clarifiers and
scum and sludge separators. TWO 8-hour composites should
be taken from the effluents from each of these points, and one
8-hour composite should betaken of scum and sludge from each
separator unit.
Compositing interval should be one hour. Three grab samples
of clean process water (city or private well) should be taken
as blanks.
Samples should betaken in50 ml bottles with gas-tight, teflon-
sealed, screw cap closures, or in equivalent containers re-
quired by the characteristics of automatic samplers. All
water, sludge, and scum samples should be refrigerated dur-
ing collection and storage. Compositing volumes should be
selected to assure head space above the sample is absent or
minimized to avoid loss of VC by its partitioning into the gas
phase when samples are sealed. Provisions should be made
to avoid such losses during continuous monitoring operations.
Estimates of discharge flows should be made using any appro-
priate measuring device (venturi, weir, magnetic meter, etc.).
Samples should be preserved by refrigeration and protected from
sunlight until they are ready for analysis.
B. Air Samples
Sampling sites should be selected which are downwind and in the
plume of the atmospheric emissions from the plant. Samples
should be collected only in areas where local residents or
neighboring industries would be exposed. At a minimum.
20
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Sampling should be conducted over a period of five days. Sites
should be selected in the following array: one site immediately
upwind (A) and one immediately downwind (B) of the plant site;
four sites about 0.4 miles from the plant site, one laterally
left (C) and one laterally right (D) of the plant site on a line
roughly perpendicular to the prevailing wind direction and two
(E, F) downwind from the plant site; two sampling sites (G, H)
approximately 0. Smiles downwind; single sampling sites, each
at distances approximately 0.6 (I), 0.8 (J), 1.0 (K), and 3.0 (L)
miles downwind from the plant site. If wind is fish-tailing
severely, move sampling sites G and H approximately 0.5 mile
upwind of the fish-tailing wind direction from the plant. The
sites specified are minimum. Additional sites may be selected
contingent on overriding micrometeorological considerations.
These should be determined in consultation with the Regional
meteorologist. These may be at ground or some elevated level,
as determined by the plume survey or as estimated by release
of meteorological balloons, anemometer, and wind direction
indicators, etc.
SAMPLING SITES
Prevailing Wind
Direction Minimum Sampling Schedule
Miles from
plant site Site Symbol Time Mon Wed Fri
0.0 A
0.4 C Plant D 0800 A,A,B A,B,B A,A,B
0.0 B 1000 C,D,F C,D C,D,D
0.4 E F 1200 A, E A,G,G A, E
0.5 G H 1400 B,B,F B, H B,B,G
0.6 I 1600 C,G E,K I, J
0.8 J 1800 D,I - L,L
1.0 K 2000 - H,L,L
3.0 L, (Note: All times are + 30 minutes for manual
grab samples, or + 2~minutes for automatic,
programmable bag~~samplers).
Grab samples should be taken in 50 ml gas-tight syringes, 50
to 100 ml glass sampling bottles, 370 ml Vacu-Sampler"
metal cans, or 12" x 12 ' capacity Tedlar-type bags. Both
the Vacu-Samplers and the glass sampling bottles should be
evacuated prior to use. (Caution: These may implode or
collapse when under vacuum. Use due care in their handling).
The perfect gas laws should be assumed to estimate gas vol-
umes. Gas-tight syringes are flushed several times with am-
bient air before a sample is taken. After the sample is taken,
the gas-tight syringe is locked and sealed until it is ready for
analysis.
21
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The Tedlar-type bag samplers may be filled by pulling the
walls of the bag apart manually, or better, by placing the
bag in an enclosure and pulling a vacuum on the outside sur-
faces of the bag. The bag is sealed until it is ready to be
analyzed. Tedlar-type bags are preferred for grab sampling.
All samples should be protected from sunlight.
Continuous Sampling - Carbon Adsorption Option:
Continuous samples are taken in pyrex tubes (approximately
3/8" O. D. x 18 ' long) packed with a good grade of activated
coconut shell charcoal. The charcoal is added to the tube
in three segments, each 3-inches long, and each separated by
a glass wool plug. The two ends of the tube are also plugged
with glass wool. Both ends of the pack adsorption tube are
plugged with serum caps during transport and for storage pur-
poses.
Flow rate through the tube is controlled by inserting a Bectoii-
Dickson 27 gage, 3/8" hypodermic needle through one of the
serum caps into the end glass wool plug. Air is sucked
through the tube by connecting it to a conventional vacuum
pump. The arrangement is similar to that used in the National
Air Surveillance Network. Flow rate should be about 200 ml
per minute. For each adsorption tube, the flow rate should
be calibrated in the laboratory before the sample is taken and
should be verified again in the laboratory after the sample is
taken. Clean needles frequently to prevent plugging.
The adsorption efficiency of the carbon in the adsorption tube
should be verified in the laboratory by preparing a 5 ppm v/v
VC mixture in the 36" x 36" Tedlar-type bag and drawing this
through the adsorption tube. Flow rates should be verified
before and after the experiment. It is important to note that
all collections should be made with the adsorption tubes held in
an upright position to minimize channeling. Adsorption tubes
should be protected from sunlight either by wrapping with foil
or by enclosing them in a box.
Each segment of the adsorption tube is worked up separately by
etching the tube in the middle of a 3" section with a file,
successively breaking each segment and spilling its contents
into measured volumes of carbon disulfide in glass stoppered
test tubes. The additions should be effected cautiously and with
cooling in an ice bath since the interaction of activated carbon
with carbon disulfide is quite exothermic. A 2 microliter
aliquot of the supernatant solution should be injected on the
carbowax 1500 column for estimation of the adsorped VC. Suc-
cessive analysis of the three adsorption tube segments will
indicate the amount of break-through of VC through the adsorb-
ent.
22
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The same procedure should be used for taking samples in
the field.
Continuous Sampling - Programmable Bag Sampler Option: The
sampler is programmed to take twenty-four consecutive one-hour
composite samples. Each one-hour sample is analyzed separately
for VC content. Sampling rate of the individual pumps should be
verified before and after use of the sampling device. Record, the
temperature and atmospheric pressure at which the samples are
taken. All gas volumes and concentrations should be corrected
to 25°C and one atmosphere (760 mm Hg). At a minimum, con-
tinuous samples should be taken at sites A, B, C, and D at
ground level, unless otherwise indicated by micrometeorological
conditions.
Calibration
A. Gas Analysis - Gas Dilution Option:
Record ambient temperature and atmospheric pressure.
Evaluate the 36" x 36" Tedlar-type bag. Add 1 liter of the
standard VC gas mixture (50 ppm, v/v) to the bag. This addi-
tion maybe made withaflow meter or with a gas-tight syringe.
Dilute with nine liters of zero nitrogen or helium carrier gas.
This gives a concentration of S.Oppm (v/v) of VC. (13 ng/ml
at 25°C and one atmosphere.)
Evacuate a 12" x 12" Tedlar-type bag and add 0. 5 1 of the 5.0
ppm (v/v) concentration mixture. Dilute with 2 liters of zero
nitrogen or helium carrier gas. This gives a concentration
of 1.0 ppm (v/v) VC, (2.6 ng/ml at 25°C and one atmosphere).
Evaucate a 12" x 12" Tedlar-type bag and add 0. 5 1 of the 1.0
ppm (v/v) VC calibration mixture. Dilute with 2 liters of zero
nitrogen or helium carrier gas. This gives a concentration
of 0.2 ppm (v/v) VC (about 0.52 ng/ml at 25 °C and one
atmosphere).
Evacuate a 12"x 12" Tedlar-type bag and add 0. 75 1 of the 0. 2
ppm (v/v) VC calibration mixture. Dilute with 1. 75 liters of
zero nitrogen or helium carrier gas. This gives a concentra-
tion of 0.06 ppm (v/v) VC (about 0.16 ng/ml at 25°C and
one atmosphere). This is about the limit of detection for direct
injection into the GC.
With a gas-tight syringe, inject 1 ml aliquots of the 5.0,
1.0, 0.20 and 0.06 ppm (v/v) VC calibration mixtures into a
GC equipped with a Carbowax 1500 or Carbopak column and
an FID detector. Use zero nitrogen or helium as carrier
gas at a flow rate of 60 ml/min. Operate the inlet and the
column isothermally at room temperature.
23
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Prepare a calibration curve. Repeat until the calibration
curve is reproducible.
B. Gas or Water Analysis - Gravimetric option:
Stock solution of VC.
Pipet 40.0 ml of carbon tetrachloride into a tared 50 ml
glass stoppered volumetric flask and accurately weigh to 0.1
mg.
Attach a tygon delivery tube to the VC lecture bottle valve.
Attach the end of the delivery tube to a piece of glass tubing
which has been constricted at one end, flush out the tube
with VC, and slowly bubble VC into the CC14 containing
volumetric flask until about 5.0 mg of VC has been added.
Precautions should be exercised to prevent loss of carbon
tetrachloride during this operation. Reweigh the volumetric
flask to determine the weight of added VC. Fill the volume-
tric flask to the 50 ml mark (approximately 100 ppm wt/vol).
(These operations should be carried out in a hood).
Transfer 1 ml of the stock solution of VC to a 25 ml volume-
tric flask and dilute to the 25 ml mark with carbon tetrachlo-
ride (approximately 4 ppm w/v).
Transfer 5 ml of the 4 ppm VC solution to a 10 ml volume-
tric flask and dilute to the 10 ml mark (approximately 2 ppm,
w/v). Repeat dilution for a solution approximately 1 ppm, and
0. 2 ppm.
Transfer the stock solution to a teflon-lined screw capped
bottle. This solution can be kept for extended periods of time
Transfer the diluted solutions to serum vials and cap them
with teflon-lined serum cap septa.
Inject 1 ml aliquots of the calibration solutions in the GC
equipped with Carbowax 1500 on Carbopak A packed columns
and an FID detector. Use Zero nitrogen or helium carrier
gas at a flow rate of 60 ml/min. Operate the inlet at 150°C
and the column at 60 °C. After the VC peak has been eluted,
program the column temperature to 150° C to elute solvent.
Cool column back to 60 °C for follow-on concentrations.
Repeat procedure using a GC equipped with a 4% FFAP on
Gas ChromQpacked column and FID detector. Operate under
the same conditions. Prepare a calibration curve to be used
be used with water samples.
24
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Procedure
Water Sample Analysis
Untreated water samples (1-5 microliter aliquots) are injected
directly into the GC.
A 4% FFAP on "Gas Chrom Q" packed column is used. Nitro-
gen zero gas or helium is used as the carrier gas at a flow
rate of 60 ml/min. Inlet temperature is set at 150°C. The
column is operated isothermally at 62°C. Detection is by FID.
Report concentration of VC in sample in mg/1.
Sludge and Scum Samples
X
Extract 5 grams of sludge or scum sample with 100 ml of
tetrahydrofuran (THF). Analyze 'THF extract in the same
manner used for water samples. If VC concentrations are
too high, make appropriate dilutions of the THF extracts.
Report concentration of VC in sample in mg /g of sample.
Air Sample Analysis
Grab samples.
Use a 0.4% CarbowaxlSOO on Carbopak A packed column. Use
nitrogen zero gas or helium as the carrier gas with a flow
rate of 60 ml/min. Operate the column and inlet at room
temperature. Use a flame ionization detector.
Untreated air samples (1 ml) are injected directly into the GC.
VC contamination of syringes requires attention.
Report concentration of VC in gas samples in ppm (v/v).
Continuous Samples
Use same procedure as previously discussed for calibration
of adsorption tube efficiency.
Quality Control
Duplicate sample analyses are recommended as a quality con-
trol check.
25
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APPENDIX V
SUMMARY OF REGIONAL ACTIVITIES
This Appendix briefly summarizes the results of the preliminary
VC monitoring activities conducted by EPA Regional Offices during the
Spring of 1974 at the request of the Task Force. More detailed reports
are available from the Regional Offices.
The sampling and analyses were carried out in a very short period
of time using new methods, based on the Agency's best scientific judge-
ment. They represent, in the Agency's opinion, the best methods
then available. In large measure, the sampling and analysis methods
were based on previous analytical studies in which similar chemicals
were evaluated. However, they had not been thoroughly tested for
accuracy and precision under field conditions.
Prior to and during the sampling and measurement only limited
quality control and standardization of procedures could be applied in
tiie time available. The methods utilized were interim procedures
which have already been subjected to further modification.
The nature of the PVC manufacturing process results in the escape
of VC pulses which could lead to widely fluctuating levels of VC in the
ambient air. So, too, changes in air movement may influence concen-
trations at a given station at any one time. Therefore, the VC data
reported are preliminary in nature and are subject to change as addi-
tional monitoring is performed. Individual measurements probably
underestimate the VC levels due to the possibility of VC leakages and
other inaccuracies in the monitoring system.
Region I: Leominster, Massachusetts: Borden Chemical Company
(PVC); May 9, 10, 13.
1. One hundred and fifty-seven discrete (grab) ambient air sam-
ples were collected on plant property and within a 3.0 mile radius of
the plant. The VC concentrations ranged from less than the detectable
limit of 0.06 ppm to 6.0 ppm. The samples exceeding 1 ppm were
obtained on plant property near the fenceline.
2. Twelve 24-hour integrated ambient air samples were collected
at the fenceline on plant property. The VC values ranged from less than
the detectable limit of 0.06 ppm to 1 ppm.
3. VC concentrations in three 24-hour composite waste water
samples taken from the lagoon effluent ranged from 0.15 to 0. 29 ppm.
4. VC concentrations in two sludge samples taken from the lagoon
near the outlet measured at the 0. 05 - 0. 06 ppm level on a wet basis.
26
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5. The plant is located in a residential/industrial area on the
edge of Leominster with residential developments adjacent to plant pro-
perty.
6. Shifting meteorological conditions and rain hampered the saiTv
pling program.
Region II: Flemington, New Jersey: Tenneco Chemicals, Inc. (PVC);
May 29-31.
1. Forty-three discrete ambient air samples were collected on
plant property and within a 2. 0 mile radius of the plant. The VC con-
centrations outside the plant property ranged from less than detecta-
ble (0.01 ppm) to 0.05 ppm. On plant property a single sample
collected on the dryer building roof contained 5.6 ppm. At ground
elevation, the VC concentrations on plant property ranged up to 0. 30
ppm.
2. Twenty-three integrated ambient air samples were collected
for 24-hour periods on plant property and within 2. 0 miles of the plant.
The VC values ranged from 0. 005 to 0.038 ppm on plant property and
from less than detectable to 0. 031 ppm outside the plant area.
3. Two integrated one-hour ambient air samples collected within
0.1 mile of the plant showed VC at levels of 0.32 ppm and 0.18 ppm.
4. A maximum level of 20 ppm was detected in three 24-hour
composite samples taken from the water effluent discharge into the
Bushkill Brook, which immediately flows into the Raritan River. This
amounts to approximately 400 Ibs/day.
5. VC concentrations in sludge samples taken from the lagoon
areas on plant property ranged from less than detectable to 1,000
ppm in wet weight concentrations; however, the concentration at the
sludge disposal area was 54 ppm.
6. The plant is located in an area in which manufacturing facili-
ties are interspersed with farmland and relatively large acreage
residential properties. There are a number of small communities
within a few miles of the plant.
Region III; Delaware City, Delaware: Stauffer Chemical Company
(PVC) and Diamond Shamrock Chemical Company (PVC);
May 20-22. S. Charleston, West Virginia: Union Car-
bide Corporation (PVC); May 24.
1. The air sampling and analysis activity was organized around
a mobile laboratory equipped with a gas chromatograph using a flame
ionization detector. VC levels were later confirmed by mass spectro-
meter.
2. A single discrete ambient air sample at the fenceline of the
Diamond Shamrock plant showed 0. 2 ppm VC.
27
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3. I-'our discrete ambient air samples taken near the Staul'l'er ('liemiral
plant ranged from 0.3 to 0.7 ppmVC. 'The highest level was recorded
0.5 miles from Hie plant and the lower levels at 0.25 miles from the
plant.
4. The area immediately adjacent to the Delaware City complex is light-
ly populated residential areas for several miles.
5. Water samples collected at the I'liion Carbide plant gave \C values
of 1.1 and 0.8 ppm for grab samples at several outfalls and 0. 35 Tor a
24-hour composite. Samples obtained from the Kanawha River did not
have a detectable level of \ C.
6. Sampling was attempted but was not feasible due to limited lime and
equipment difficulties at the P\ C plants of the Firestone Plastics Company
in Perryville, Maryland, and Pottstown, Pennsylvania.
Region IV: Louisville, Kentucky: R. F. C.oodrieh Chemical Company
(PVC); March 19-21 and May 8-16.
1. The initial air monitoring program conducted in March was pre-
liminary to the more extensive program in May which showed significant-
ly higher levels.
2. In May there were 39 discrete ambient air samples collected in
the area designated industrial (within 0.8 miles from the plant center).
The VC concentrations ranged from less than 0.05 to 5.6 ppm, with 10
samples exceeding 1 ppm. In the area designated residential/ industrial,
149 samples were collected within 0. 8 miles of the plant with VC concen-
trations ranging from less than 0.05 to 33 ppm. The average concentra-
tions at the site registering 33 ppm were between 0.5 and 1 ppm, but 18
samples had concentrations greater than 5.0 ppm. Four samples were
obtained in strictly residential areas with VC values of 0.05 to 1.6 being
observed. The 1.6 value was 0.8 miles from the plant.
3. Five sampling sites were established within 0.6 miles of the plant
for integrated air sampling over 24 hours. VC values ranged from less
than 0.001 to 0.53 ppm. The highest value was obtained from a sampling
site 0.2 miles from the plant center,
4. Wastewater from the clarifier discharge was measured in March
at 2 to 3 mg/1 in 24-hour composite samples.
5. Dewatered clarifier sludge and clarifier scum contained 193 and 162
ppm of VC, respectively.
Region V: Painesville, Ohio: Uniroyal, Inc. (PVC) and Robintech, Inc.
Inc. (PVC); May 9-14.
1. Four of 137 ambient air samples taken at distances up to 3,0 miles
from the plant showed levels exceeding 1 ppm of VC with the highest level
being 2. 26 ppm. Many of the samples were less than 0.1 ppm.
28
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2. Nine 24-hour integrated ambient air samples taken at various dis-
tances from the plant showed levels up to 0. 2 ppm of VC.
3. VC levels in 11 of 17 water effluent samples were less than 0. 2 ppm,
with three samples exceeding 1 ppm, including a high of 3. 7 ppm.
4. VC levels in nine sludge samples, as the sludge would leave the
plant property, ranged from 9 to 3520 ppm.
5. The complex is surrounded by residential areas.
Region VI: Plaquemine, Louisiana: The Goodyear Tire and Rubber
Company (PVC) and Dow Chemical Company (VC); April 7-9.
1. There were 31 discrete ambient air samples collected within 3.0
miles of the complex with VC concentrations ranging from less than detec-
table (.001 ppm) to 7. 81,ppm. Most of the readings were less than 1 ppm,
with the highest value at the property line.
2. VC concentrations in wastewater effluent measured by 24-hour com-
posites were all below . 05 ppm.
3. VC concentrations in residual reactor scrapings at the Goodyear
plant ranged from 23 to 31 ppm.
4. The small communities of Morrisonville and Eliza are located
less than 1 mile north and northwest respectively of the Goodyear plant.
A few homes from Morrisonville extend almost to the north property line
of the Goodyear plant.
5. Very limited air sampling was conducted in the Houston area in the
vicinity of the plants listed below. However, in view of the inadequacy of this
activity, the sampling effort in this area is being continued.
Deer Park, Tex., PVC Plant - Diamond Shamrock Corp., Diamond Sham-
rock Chemical Co.
Deer Park, Tex., VC Plant - Shell Chemical Co., Industrial Chemicals
Division
Houston, Tex., VC Plant - Tenneco, Inc., Tenneco Chemicals, Inc.
Pasadena, Tex., VC Plant - Ethyl Corporation
Region IX: Long Beach, California: B.F. Goodrich Chemical Company
(PVC); American Chemical Corporation (VC); American Chem-
ical Corporation (PVC); May 7-10.
1. One hundred and eighty 10-minute integrated ambient air samples
were collected within 3.1 miles of the complex. About 11 percent of the
29
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readings exceeded 0.5 ppm, while 5 percent exceeded 1.0 ppm. The
maximum value measured was 3.4 ppm in a sample taken 3.1 miles from
the plant; however, the average level measured at this point was about
0. 5 ppm.
2. Samples of wastewater effluents were composited for 8 to 24
hours and yielded values from 3.5 to 8.9 ppm, with individual samples
reading up to 22 ppm.
3. Sludge samples showed values ranging from 290 to 4200 micro-
grams of VC per gram of dry sludge.
4. The complex is surrounded by residential areas. Within the
three mile radius of the plants there are eleven schools.
30
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PERSISTENCE OF VINYL CHLORIDE
The available information on the stability and persistence of YC in
the environment is currently very limited. Some literature and laboratory
studies have recently been initiated by industry and by EPA. This discus-
sion summarizes the findings of EPA to date and particularly the results
of research efforts at EPA research facilities undertaken in response to
the needs of the Task Force for at least preliminary data on environmental
fate. Results of related experiments reported by industry seem 10 be
consistent with the discussion.
Behavior of Vinyl Chloride in Air
The peak absorption of VC in the ultraviolet region is very far below
the solar cutoff of about 2900 A, indicating that VC would not undergo
reaction in sunlight in the absence of other reactive chemicals. When
irradiated with simulated solar radiation in the presence of nitrogen
oxides (nitric oxide and nitrogen dioxide), VC reacts to form a variety
of products. The available laboratory results indicate a rate of reaction
of about 8 to 10% per hour for VC, recognizing that reaction rates may
vary with concentrations. The direct and indirect reaction products
identified included ozone, nitrogen dioxide, carbon monoxide, formalde-
hyde, formic acid, and formyl chloride. High eye irritation levels were
found with human exposure panels which is consistent with the products
identified.
The low reaction rate of VC, including reactions in the presence of
nitrogen oxides, indicates that within a few miles downwind of VC emission
sources VC will persist and can be considered a stable pollutant. The
usual meteorological dispersion equations for gases could be applied to
approximate concentrations. Because of temperature inversions and the
absence of sunlight at night during the fall and winter, buildup of VC
might be of particular concern during such periods. Clearly at greater
distances from emission sources, VC will have greater opportunity to
disperse and degrade.
The noxious gases which are products of VC reactions should not be
ignored. In air quality regions with large industrial activities involving
large volume production of these chemicals, such products may contribute
appreciably on particularly sunny days to eye, nose, throat, and lung irri-
tation.
Behavior of Vinyl Chloride in Water
The loss of VC from water at constant temperature and pressure de-
pends on the rate of agitation or aeration. Distilled water in a. beaker
spiked with 16 ppm VC, when rapidly stirred at 22°C with a magnetic
stirrer, lost 96% of -VC in two hours, while quiescent water at the same
concentration lost only 25% VC. There was no significant difference in
the rate of VC losses from distilled water, river water, or effluent from
a VC plant stirred at the same rate, indicating negligible adsorption
effects with particulate matter. Plots of log water concentration versus
time give straight lines, indicating volatility to be the only important loss
mechanism.
31
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Hydrolysis over a pH range of 4.3 to 9.4 does not appear to be an im-
portant pathway for loss of VC from water. Chemical reaction of VC in
the clarifier effluent from a VC plant was followed at 50°C for 57 hours
at pH 4.3, 8.0, and 9.4 in sealed septum vials. Concentrations indicated
that VC at these three pH values decreased at the same rate. This lack
of pH dependence suggests that the loss of VC occurred by volatilization
rather than hydrolysis, or at least there is a very slow hydrolysis rate.
This experiment should be repeated in leak-proof reaction vials.
Very preliminary experiments do not show photolysis as an impor-
tant pathway for loss of VC in water. However, there are many uncertain-
ties in the experimental techniques, and additional studies are needed in
this area.
Earlier theoretical studies are consistent with these experimental re-
sults. One study on the transfer of small non-reactive molecules across
the air-water interface (as in stream aeration) used a kinetic approach
to predict that VC will be rapidly lost from an aqueous solution, with the
rate of loss being a function of water turbulence, mixing efficiency, and
molecular diameter. Another study, using a thermodynamic approach,
predicted a rapid rate of evaporation of low solubility chlorinated hydro-
carbons, including compounds of low vapor pressure.
Despite the foregoing efforts there is a general absence of data con-
cerning VC in aquatic systems. It is conceivable that as the result
of poor or erratic mixing in lakes or ponds, together with slow but con-
tinuous release of VC from sediments and sludges, VC could persist
long enough to accumulate biologically, via direct absorption or via the
food chain, or to cause other ecological effects.
Behavior of Vinyl Chloride in Closed Rooms
Tables 1 and 2 present data concerning concentrations of VC in a
typical room following release of a pesticidal spray containing VC.
TABLE 1
One Hundred and Twenty Second Release of Insect Spray in
133, 000 Liter Room
SAMPLE
TIME
VC
COLUMN I
FREON-12
VC
COLUMN II
FREON-12
No. 1 Collected at
breathing zone
during spray
No. 2 15 minutes
No. 3 30 minutes
No. 4 60 minutes
No. 5 120 minutes
41.64ppm 8.15ppm
41.9 ppm 7.94 ppr
16.91
1.38
0.08
0.012
3.13
0.27
0.018
17.1
3.30
1.32 0.25
0.061 0.018
0.010
32
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TABLE II
Thirty Second Release of Insect Spray in 21,400 Liter Room
COLUMN I COLUMN II
SAMPLE TIME
No.
No.
No.
No.
No.
I
2
3
4
5
Collected one
minute after
spray
30 minutes later
60 minutes
150 minutes
Collected in
adjacent hall
151 minutes
VC
380.
52.
24.
10.
0.
1 ppm
1
6
3
83
FREON-12*
84. 8 ppm
9.9
4.8
2. 1
0.17
VC I
383
48
22
9.
0.
. 6 ppm
. 7
.5
3
17
'REON-12*
83.
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4.
2.
0.
2
3
7
2
ppm
15
*Freon-12 concentrations were determined using hydrocarbon response factors
to compare dilution effects; the actual concentration is higher by a factor of 5.3.
REFERENCES
1. Unpublished results of experiments and analyses conducted at EPA
laboratories in Research Triangle Park, N. C. , and Athens, Georgia,
during April and May 1974,
2. Unpublished results of experiments on persistence of VC in water
conducted by Dow Chemical Company.
3. Tsiroglou, E. C. and J. R. Wallace, "Characterization of Stream
Reaeration Capacity, " EPA Ecological Research Series Report #EPA-
R3-72-012 (October, 1972).
4. MacKay, Donald and Aaron W. Wolkoff, "Rate of Evaporation of Low-
Solubility Contaminants from Water Bodies to Atmosphere, " Environ-
mental Science & Technology. 7 (7);611-614 (July, 1973).
33
-------
APPENDIX VII
HEALTH EFFECTS OF VC
This Appendix presents much of the epidemiological and toxi-
cological data available as of August 1974, on the health effects
associated with exposure to VC, together with a few interpretive com-
ments supplementing information presented in the body of the report.
However, the Appendix does not present an exhaustive review or
evaluation of available information.
Table 1 summarizes the data, collected by CDC/NIOSH, on the
confirmed cases of angiosarcoma of the liver in VC/PVC workers in
the United States and abroad. A total of 15 occupational cases have
been discovered in the United States and confirmed as angiosarcoma
of theliver. Of the 15 cases, 2 are still alive and undergoing treat-
ment. Fourteen of the 15 were employed in PVC production plants and
the remaining one in a PVC fabrication plant. The average age at
death for the U.S. PVC production workers was 48.5 years (with a
range from 36 to 61 years) which is about seven years younger
than the average age of death from liver cancer in the U. S. male
population. Based on the data available for the workers, the latent
period for this disease appears to be on the order of twenty years,
a period consistent with latencies observed for other occupational,
chemically induced cancers.
In the U.S. PVC production worker cases, all of the men were
at one time "pot cleaners", required to enter the reactors in order
to chip the residue of the chemical reaction from the sides of the
"pots." Since the residue often contained pockets of trapped
gases that were literally released in the cleaner's face when they
were ruptured by his chipping operation, the potential for exposure
to high levels of VC while cleaning these tanks was particularly
great during the early years of this operation.
Ten cases of worker-related angiosarcoma of the liver have
been reported from five foreign countries to date.
Table 2 summarizes the epidemiological data, collected by
CDC from the Connecticut Tumor Registry, on five confirmed cases
of angiosarcoma of the liver, including one accountant in a PVC
fabrication plant and two residents near PVC fabrication plants.
The case of occupational exposure occurred in a man who had been
employed for 10 years as an accountant in a factory which pro-
duces vinyl sheets and processes PVC resins; it is reported that
he frequently visited the production area of the plant. Of the two
cases who had no occupational exposure to VC or PVC, one was a
73 year-old man "who lived his entire life within two miles of a PVC
wire insulation plant. The other was an 83 year-old woman, a
housewife and retired cook, who had lived for 35 years within
one-half mile of the vinyl products plant at which the accountant
had been employed.
34
-------
While these findings establish no causal connection between
exposure to PVC and angiosarcoma of the liver, they do raise the
ossibility of such a relationship. Time will Be needed to define
e possible risk factors in persons who have worked with PVC
stince the latency period appears to be so long. Because of the rarity
of this tumor, the additional finding in this study of angiosarcoma of
the liver in persons who had no occupational exposure to VC, but
who may have had community exposure, is also worrisome but again
establishes no causal connection. Epidemiologic investigation of
additional cases of hepatic angiosarcoma that may be found to have
had possible community exposure to VC will be necessary to clarify
the significance of these cases.
Tables 3A - 3D present the findings of the MCA-funded mortality
study of VC/PVC workers, conducted by Tabershaw/Cooper Asso-
ciates.
In calculating the risk of death, the usual method is to express the
number of deaths which actually occurred as a percentage of the
number which would have been expected in a comparable population
observed over the same age and time intervals. This statistic is
called the Standardized Mortality Ratio (SMR). Using the U.S. male
population as the standard population of comparison, the SMRs were
calculated for each of the 35 cases of death for which detailed mor-
taility rates are published on a national basis. In the standard
population each SMR would be equal to 100. The statistical signifi-
cance of the deviation of each SMR in the study population from the
expected value of 100 was tested. A single asterisk indicates those
SMRs which differed significantly from 100 at the 5 percent level,
that is, which had a probability of . 05 or less of occurring by chance.
A double asterisk indicates those which were significant at the 1
percent level. SMRs based on fewer than 5 observed cases were
not tested for significance. The overall mortality of the study
population is statistically significantly lower than that of the U. S.
male population. There were 352 observed deaths compared with
467 expected, for an SMR of 75.
For each job, an exposure score was estimated by industrial hy-
giene and safety personnel in each plant. A score of 1 was given
for low exposure, 2 for medium, and 3 for high. The number of
months each worker spent on a given job was multiplied by the appro-
priate exposure score. The total for each worker was then divided
by the total number of months of exposure to give an Exposure Index
(El) for that worker. Table 3A shows the SMRs for workers with an
El below 1. 5 versus those at 1. 5 or above. The dividing point of 1. 5
represents a level halfway between low and medium exposure. Table
3B shows similar results for workers with less than 5 years exposure
versus those with 5 years or more.
In order to examine the possible interaction between duration and
level of exposure, the study population was divided into 4 groups on the
basis of both El (low vs. high) and duration of exposure (short vs.
35
-------
long) using the same dichotomization as Tables 3 A and 3B. Table 3C
shows the results for short versus long exposure in the low El group,
and Table 3A shows the same comparison in the high El group. When
the study population is divided according to length and duration of
exposure (Tables 3A and 3B) and combinations of these measurements
(Tables 3C and 3D), three major patterns emerge. For malignant
neoplasms as a whole, the SMR increases with increasing exposure,
whether measured by level, duration, or both. In the high exposure
group with 5 years or more exposure (Table 3D) there are 36 observed
cases and 26.11 expected. For cardiovascular - renal diseases as a
group, there are also increases in the SMR with increasing exposure,
but the number of observed cases remain less than expected, the
differences being statistically significant in all groups except the high
exposure, long duration group. For all other causes, there are no con-
sistent relationships with exposure.
Within the malignant neoplasms, the largest (although not statisti-
cally significant) SMR is in cancers of the buccal cavity and pharynx,
with 5 observed, 2.84 expected, and an SMR of 189. However, Tables
3A and 3D show that all these cases have an El below 1.5, and 4 out
of 5 have less than 5 years exposure.
Cancer of the digestive system shows no excess in the study popu-
lation asa whole. However, in those workers with Els of 1.5 or higher,
there are 12 observed cases where 9.14 are expected (Table 3A). In the
subgroup of the above workers with 5 years or more exposure, there are
11 observed cases and 7.47 expected.
Respiratory cancer shows a slight excess in the total group, and a
similar pattern for different exposure categories, with 13 observed
versus 10.28 expected when the El is 1.5 or higher, and 12 observed
versus 8.50 expected when, in addition, the duration of exposure is 5
years or more.
Malignant neoplasms of other and unspecified sites show an excess
in the total group, and an increase with both level and duration of
exposure (Tables 3A and 3B). The relationship with exposure is more
pronounced, since those with exposures of less than 5 years have fewer
cases than expected.
The lymphosarcomas, although occurring at about the expected
rate when the whole group is considered, are concentrated almost
entirely in the high exposure long duration group. In that category
there are 4 cases observed and 1.84 expected.
The Tabershaw/Cooper Study is based on an examination of 328
death certificates. The authors acknowledge three areas where bias
might have entered: (a) choice of the U. S. male population as the
36
-------
standard, (b) absence of 15% of the study population (untraccable),
and (c) discovery, as the study ended, of a group of 1500 workers
whose exposures occurred up to 35 years ago and who are not included
in the study group. Since the latency period fo r angiosarcoma of the
liver is averaging 18 years at least, it would appear desirable
to examine the data for these 1500 workers.
In addition to the Tabershaw/Cooper study several other epidemio-
logical studies presented during the recent OSHA hearings suggest the
possibility of a multiple cancer risk.
Table 4 summarizes many of the published and unpublished toxi-
cological and epidemiological studies of human and animal exposures
to VC. A list of the references cited in Table 4 completes this
Appendix.
37
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59
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REFERENCES
Baretta, E.D., R. D. Stewart, and J.E. Mutchler. Monitoring Expo-
sures to Vinyl Chloride Vapor: Breath Analysis and Continuous Air
Sampling. American Industrial Hygiene Association Journal, Volume 30,
pp. 537-544.
Basalaev, A.V., A.N. Vazin and A.G. Kochetkov. Pathogenesis of
Changes Developing Due to Long-term Exposure to the Effect of Vinyl
Chloride. GIG TR Prof Zabol 16 (2) : 24-27. 1972.
Clapp, J.J., C.M. Kaye, and L. Young. Metabolism of Alkyl Com-
pounds in the Rat. Biochem. Journal 114(1), pp. 6-7. 1969.
Dinman, B.D., W. A., Cook, W.M. Whitehouse, H. J. Magnuson, and
T. Ditcheck. Occupational Acroosteolysis: I. An Epidemiological Study.
Archives of Environmental Health, Volume 22, pp. 61-73, January, 1971.
Dodson, V.N., B.D. Dinman, W.M. Whitehouse, A.N.M. Nasr, and
H. J. Magnuson. Occupational Acroosteolysis: III. A Clinical Study.
Archives of Environmental Health, Volume 22, pp. 83-91, January 1971.
Gabor, S., M. Lecca-Radu, and I. Manta. Certain Biochemical Indexes
of the Blood in Workers Exposed to Toxic Substances (Benzene, Chloroben-
zene, Vinyl Chloride). Prom. Toksikol. i Klinika Prof. Zabolevanii Khim.
Etiol. Sb. 221-223. 1962.
Gabor, S., M. Radu, N. Preda, S. Abrudean, L. Ivanof, Z. Anea, and
C. Valaezkay. Inst. Hyg. Cluj., Romania. Bucharest 13 (5), 409-418.
1964.
Grigorescu, I. and G. Tova. Vinyl Chloride; Industrial Toxicological As-
pects. Rev. Chim. 17(8): 499-501. 1966.
Harris, D.K. and W.G.F. Adams. Acroosteolysis Occurring in Men En-
gaged in the Polymerization of Vinyl Chloride. Brit. Med. Journal, 5567,
pp. 712-714. nius. 1967.
Kramer, C.G., and J.E. Mutchler. The Correlation of Clinical and En-
vironmental Measurements for Workers Exposed to Vinyl Chloride.
American Industrial Hygiene Association Journal, Volume 33(1): 19-30.
1971.
Kudryavtseva, O.F. Characteristics of Electrocardiographic Changes in
Patients with Vinyl Chloride Poisoning. GIG TR Prof Zabol 14(8):54-56.
Kuebler, H. The Physiological Properties of Aerosol Propellants. Aero-
sol Age 9(4), 44,47-48, 50, 90-91. 1964.
Lange, C.E., S. Juhe, G. Stein, and G. Veltman. Uber die Sogenannte
Vinylchlorid-Krankheit. Dtsch. med. Wschr. 98, pp. 2034-2037. (Ger-
man) 1973.
60
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Lester, D., L.A. Greenberg, and W. R. Adams. Effects of Single
and Repeated Exposures of Humans and Rats to Vinyl Chloride. Amer-
ican Industrial Hygiene Association Journal, pp. 265-275, May-June,
1963.
Maltoni, C. Preliminary Report on the Carcinogenicity Bio-as says
of Vinyl Chloride. Presented at OSHA Vinyl Chloride Fact Finding
Hearing, February 15, 1974.
Markowitz, S. S., C.J. McDonald, W. Fethiere and M.S. Kerzner.
Occupational Acroosteolysis. Arch Dermatol 106 (2):219-223. 1972.
Marsteller, H. J. Chronic Toxic Liver Damage in Workers Engaged in
PVC Production. Deutsche Medizinische Wochenschift 98 2311-2314.
1973.
Mastromatteo, E./ M.D., A.M. Fisher, H. Christie, and H. Dan-
ziger. Acute Inhalation Toxicity of Vinyl Chloride to Laboratory Ani-
mals. American Industrial Hygiene Association Journal, Volume 21,
No. 5, October, 1960.
Meyerson, L. B. and G.C. Meier. Cutaneous Lesions in Acroosteoly-
sis. Arch Dermatol 106(2):224-227. 1972.
Torkelson, T.R., F. Oyen, and V.K. Rowe. The Toxicity of Vinyl
Chloride as Determined by Repeated Exposure of Laboratory Animals.
American Industrial Hygiene Association Journal, Volume 22, No. 5,
pp. 354-361. 1961.
Vazin, A.N. and E.I. Plokhova. Creation of an Experimental Model
of "toxic angioneurosis" Developing from the Chronic Action of Vinyl
Chloride Vapors on an Organism. GIG TRProf Zabol 12(7):47-49. 1968a.
Vazin, A.N., E.I. Plokhova. Pathogenic Effect of Chronic Exposure to
Vinyl Chloride on Rabbits. Farmakol Toksikol, 31(3):369-372. 1968b.
Vazin, A. N., and E.I. Plokhova. Dynamic Changes in Epinephrine-
like Substances in Rabbit Blood Following Chronic Exposures to Vinyl
Chloride fumes. GIG TR Prof Zabol 13(6):46-47. 1969a.
Vazin, A. N., E.I. Plokhova. Changes in the Cardiac Activity of Rats
Chronically Exposed to Vinyl Chloride Vapors. Farmakol Toksikol, 32(2):
220-222. 1969b.
Viola, P.L. Pathology of Vinyl Chloride. Medicina del Lavoro, Vol-
ume 61, No. 3 March, 1970. Translated from the Italian. 1970a.
Viola, P.L. The Vinyl Chloride Disease, (unpublished translation) Sum-
mer, 1970.
Viola, P. Lo, A. Bigotti, and A. Caputo. Oncogenic Response of Rat
Skin, Lungs, and Bones to Vinyl Chloride. Cancer Research, Volume 31,
pp. 516-522.
61
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Von OettLngen, W. F., M.D. The Halogenated Aliphatic, Olefinic,
Cyclic, Aromatic, and Aliphatic-aromatic Hydrocarbons including the
Halogenated Insecticides ,Their Toxicity and Potential Dangers. Public
Health Service Publication No. 414, U. S. Department of Health, Edu-
cation, and Welfare, Washington, D. C. 1955.
Wilson, R. H., W. E. McCormick, C.F. Tatum, andJ.L. Creech.
Occupational Acroosteolysis, Report of 31 Cases. The Journal of the
American Medical Association, Volume 201. No. 8, pp. 577-581. 1967.
62
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APPENDIX VIII
DISPOSAL OF PRODUCTS CONTAINING POLYVINYL CHLORIDE
This discussion on disposal of PVC emphasizes incineration and
landfilling, the only presently used large-scale methods for the disposal
of solid wastes. There is also a limited discussion of resource recovery
possibilities.
Incineration
The two areas of concern related to PVC incineration are incinerator
air pollution and incinerator and gas scrubber corrosion.
Hydrogen chloride is the major toxic material released when PVC is
burned. It has been shown that virtually all of the chlorine is released
from PVC on combustjon, resulting in HC1. It is estimated that 0. 2 per-
cent of solid waste is PVC, and 16 x 10^ tons per year of solid waste are
incinerated in the United States. Thus, on the order of 32,000 tons of
PVC are burned annually, releasing approximately 18,500 tons per year of
HC1 as air emissions.
Other solid waste sources which can produce HC1 are chlorides in
food waste, plants, grass clippings, and inorganic salts. The formation
of compounds requires volatilization and reaction with incinerator flue
gases. Achinger and Baker compiled data indicating an emission factor of
six pounds of HC1 per ton of solid waste burned. Recent data on HC1
emissions obtained by Battelle show a factor of 5.1 pounds per ton. A
value of five to six pounds per ton would be a reasonable emission factor
to use for HC1 emissions from municipal incinerators. Using an emission
faotor of 5.5 pounds per ton gives 44,000 tons per year of HC1 produced
by incineration of municipal solid waste. The amount of HC1 produced
from PVC using the above calculation is 42 percent of the total.
Much more HC1 is probably now emitted to the atmosphere from the
nation's coal-burning power plants than from our municipal incinerators.
However, there still could be a hazard in the immediate vicinity of an
incinerator as a direct result of its HC1 emissions. Of particular concern
is the possible dispersal of the stack gases to cause the ambient concen-
trations of HC1 at ground level to exceed harmful concentrations. How-
ever, HC1 is not at the present time regulated by EPA.
Other air pollutants could be formed from the additives in PVC dur-
ing incineration. Several additives are usually incorporated into the poly-
mer to emphasize particular properties not inherent in the base polymer.
The types of additives are antioxidants, antistatics, colorants, fillers,
plasticizers, and stabilizers. Some of the additive agents used are: anti-
oxidants--phenols, amines, phosphates, and sulfur compounds; antistatics
--amine derivatives, quaternary ammonium salts, phosphate esters,
63
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polyethylene glycolesters; colorants--salts or oxides of metals, aluminum,
copper and inorganic pigments; fillers--silica, glass, calcium carbonate,
metallic oxides, carbon, cellulose fillers, asbestos; plasticizers--phthal-
ates, organic phosphates; stabilizers--lead salts of acids, barium, cad-
mium, calcium, zinc, alkyl tin compounds.
It is highly unlikely that large quantities of VC will be emitted during
incineration of PVC. There is no evidence that PVC will chemically revert
to VC. Some small amounts of entrapped monomer might conceivably
survive incineration, but these quantities would be very low.
The second area of concern with incineration of PVC is firebox corro-
sion and corrosion of pollution control equipment. HC1 can be a major
factor related to corrosion of this equipment during incineration at certain
temperatures. In the case of plastics, PVC is the major source of chlorine
leading to HC1, but other plastics may also contain some chlorine.
Incinerators with heat exchangers will have corrosion problems on the fire
side of the exchange equipment when the combustion gases contact the outer
metal surface. Other surfaces of concern are in the cooling area and in the
gas scrubbers.
Estimates indicate that in incinerators with heat-recovery systems
PVC in the refuse will increase tube maintenance costs by 15 to 20 per-
percent over that to be expected if PVC-free refuse was used as fuel.
About 95 percent of the incinerators in this country have some type
of air pollution control equipment that is exposed to the high chloride envi-
ronment resulting from refuse combustion. Because of the high chlorine
content of the combustion products, the cooling and precipitating water
from the scrubbers that contacts the flue gas contains large quantities of
chloride and is extremely corrosive to the structure.
In summary, technology exists for controlling the HC1 emissions
that result from incineration of solid waste; however, the application of
this technology will resultin increased costs. If technology is not applied,
then the contribution of PVC to the nation's air pollution problem will
increase because of the projected increases in the usage and disposal.
HC1 scrubbing technology is available, but its application results in corro-
sion problems. Depending on construction materials, design, and opera-
tion, these problems can be either large or small.
Landfilling
PVC does not decompose significantly within the normal time frame
of most other municipal solid wastes. It comprises only about 0.2 percent of
the total municipal solid waste being landfilled today, and the effect of PVC
on the reuse of the landfill site, at least in the short run, should be negligi-
ble.
64
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Since PVC degrades very slowly, in the landfill environment it should
not add significantly to the production of leachate or decomposition gases
as do other parts of the refuse. The additives of greatest concern are
probably the plasticizers. However, if a sanitary landfill is designed and
operated with today's technology, disposal of PVC products in a sanitary
landfill should pose no special problems to the operation or to the ultimate
use of the site.
Resource Recovery
Recycling of solid waste is a growing industry. Technology has been
developed to recover some resources from many of the items in the
municipal waste stream. However, the technology to separate plastics or
PVC from the waste stream has not yet been commercially demonstrated.
The solution to the separation of plastic waste from other components of
the municipal waste stream is one deterrent to direct recycling and reuse
of plastics, including PVC. However, gathering and centralizing the waste
products are also major problems.
Some types of scrap PVC from the fabrication process are presently
being recycled back into the manufacturing process. This reduces the solid
waste from plastic fabrication plants and reduces the need for new raw
materials.
There is work underway to develop means for utilizing the benefits
of recycling the total municipal waste stream. Examples of these recycling
techniques are listed below:
. -- To recover heat given off during the incineration of solid waste
containing PVC and other combustible materials as electricity or
steam for heating. An example is EPA's research contract with
the Combustion Power Company of Menlo Park, California, in
which combustion gases are expanded through a turbine to produce
power.
- - To recover the products of a refuse pyrolysis operation either
as a pipeline gas or as feed material for a nearby refinery.
An example is EPA's research grant with West Virginia University
in which refuse pyrolysis is being studied on a bench-scale. A
second example is the Bureau of Mine's research effort to convert
refuse to pipeline gas. Also, US and Japanese industrial firms
are actively exploring this area.
The recent change in the world's supply of crude oil should speed up
research and development on new and existing ways to utilize more fully the
resource of waste PVC.
65
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REFERENCES
1. E.A. Boettner, G.L. Bell, B. Weiss, "Combustion Products from tl
Incineration of Plastics, "Report No. EPA-670/2-73-049, July 197
2. "Compilation of Air Pollution Emission Factors," 2nd Editioi
. Publication No. AP-42, EPA, April 1973.
3. W.C. Achinger and R. L. Baker, "Environmental Assessment of Mur
cipal-Scale Incinerators, " Report No. SW-111, EPA, 1973.
4. G.L. Huffman, "The Environmental Aspects of Plastics Waste Trea
ment," Symposium on the Disposal and Utilization of Plastics, Ne
Paltz, New York, June 25, 1973.
5. "Threshold Limit -Values, " American Conference of Governmental ar
Industrial Hygienists, 1972.
6. Fessler, R., H. Leib, H. Spahn, "Corrosion in Refuse Incineration
Plants, " Mitt. Ver. Grosekesaelbets, 4£ 126 - 140, April 1973.
7. Vaughan, D.A., and P. D. Miller, "A Study of Corrosion in Municipz
Incinerators," Cincinnati, Research Grant, April 1973.
8. Miller, P.D. et al, "Corrosion Studies in Municipal Incinerators,
SHWRL - NERC, Report SW - 72-3-3.
9. Baum, B. and C. H. Parker, "incinerator Corrosion in the Presenc
of Polyvinyl Chloride and Other Acid-Releasing Constituents," repor
. by DeBell and Richardson, Inc. (No date)
10. George L. Huffman and Daniel J. Keller, "The Plastics Issue, " SHW:
NERC, Cincinnati, Ohio,.. August 28, 1972.
11. "Incinerator Gas Sampling at Harrisburg, Pennsylvania, " EPA Co
tract No. 68-02-0230, Office of Air Programs, September 1973.
66
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APPENDIX IX
ACTIVITIES OF TASK FORCE
The principal activities undertaken or stimulated by the Task Force are
set forth below:
MARCH - Recognition of problem of pesticidal sprays containing VC--
Responsibility assigned to Office of Pesticide Programs
MARCH - Analysis of material losses during PVC polymerization pro-
cess
MARCH 19-21 - Pilot monitoring effort at B. F. Goodrich Plant in Louisville
MARCH - Preliminary evaluation of health effects data
APRIL 2 - Meeting" with representatives of PVC manufacturers organ-
ized by Manufacturing Chemists Association
APRIL 4 - Meeting with representatives of interested environmental
groups
APRIL - Development of interim methodology for VC sampling and
analysis
APRIL/MAY - Visits to VC manufacturing facilities and to PVC polymeri-
zation, compounding, and fabrication facilities
APRIL 12
APRIL/MAY
- First of series of interagency meetings convened by EPA
- Monitoring at seven complexes involving 10 PVC and 2 VC
plants
APRIL/MAY - Review of health effects data
APRIL 30 - Review of Industrial Bio test toxicological experiments
- Preliminary VC water persistence studies
Preliminary VC air persistence studies
MAY 27-31
MAY
MAY/JUNE
- Recognition of air emissions problem -- Responsibility
assigned to Office of Air Quality Planning and Standards
JUNE 3 - Technical review of monitoring activities
JUNE 11 - Administrator1 s meeting with senior executives of 29 com-
panies producing PVC and VC
JULY - Development of improved methodology for VC sampling and
analysis
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