EPA-650/4-7 5-020
Environmental Monitoring Series
AIR MEASUREMENTS
OF VINYL CHLORIDE
IN THE NIAGARA FALLS AREA
01
O
U.S. Environmental Protection Agency
Office of Research and Development
National Environmental Research Center
Research Triangle Park, N. C. 27711
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EPA-650/4-75-020
AMBIENT AIR MEASUREMENTS
OF VINYL CHLORIDE
IN THE NIAGARA FALLS AREA
by
Bruce W. Gay, Jr., and Richard C. Noonan
Chemistry and Physics Laboratory
Program Element No. 1AAOOA
ROAP No. 21AKC
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
National Environmental Research Center
Research Triangle Park, North Carolina 27711
May 1975
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EPA REVIEW NOTICE
This report has been reviewed by the National Environmental Research
Center - Research Triangle Park, Office of Research and Development,
EPA, and approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the Environmental
Protection Agency, nor does mention of trade names or commercial
products constitute endorsement or recommendation for use.
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environ-
mental Protection Agency, have been grouped into series. These broad
categories were established to facilitate further development and applica-
tion of environmental technology. Elimination of traditional grouping was
consciously planned to foster technology transfer and maximum interface
in related fields. These series are:
1. ENVIRONMENTAL HEALTH EFFECTS RESEARCH
2. ENVIRONMENTAL PROTECTION TECHNOLOGY
3. ECOLOGICAL RESEARCH
4. ENVIRONMENTAL MONITORING
5. SOCIOECONOMIC ENVIRONMENTAL STUDIES
6. SCIENTIFIC AND TECHNICAL ASSESSMENT REPORTS
9. MISCELLANEOUS
This report has been assigned to the ENVIRONMENTAL MONITORING
series. This series describes research conducted to develop new or
improved methods and instrumentation for the identification and quanti-
fication of environmental pollutants at the lowest conceivably significant
concentrations. It also includes studies to determine the ambient concen-
I rations of pollutants in the environment and/or the variance of pollutants
as a function of time or meteorological factors.
This document is available to the public for sale through the National
Technical Information Service, Springfield, Virginia 22161.
Publication No. EPA-650/4-75-020
11
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CONTENTS
INTRODUCTION 1
EXPERIMENTAL 2
RESULTS 3
DISCUSSION AND CONCLUSIONS 5
REFERENCES 8
TECHNICAL REPORT DATA SHEET . . .15
111
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AMBIENT AIR MEASUREMENTS
OF VINYL CHLORIDE
IN THE NIAGARA FALLS AREA
INTRODUCTION
Vinyl chloride is a synthetically produced colorless gas that
is polymerized to polyvinyl chloride and made into a variety of
plastic products. Health studies of employees at vinyl chloride
and polyvinyl chloride plants have shown that exposure to vinyl
chloride can cause rare angiosarcoma of the liver, cancers in
1-4
other tissues, and other damage to both the liver and spleen.
Occupational instances of liver angiosarcoma have occurred primarily
among workers exposed to extremely high levels of vinyl chloride. Am-
bient air concentrations of vinyl chloride are, of course, much lower
than those found in industrial atmospheres; however, it is not known
if there is a concentration limit below which no adverse health effects
occur even when people are exposed for long periods of time.
At the Niagara Falls Goodyear Tire and Chemical Plant, three
cases of angiosarcoma of the liver have been reported among workers.
The plant produces vinyl chloride resins by emulsion and suspension
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polymerization processes. The emulsion process was used first and
began operation in 1946. The plant is located on the eastern edge
of an industrial chemical complex. Hooker Chemical and other chemical
companies in the complex also produce various halogenated organic com-
pounds, chlorine, and polymers. Residential areas are located to the
northeast, north, and east-south east of the chemical complex in
Niagara Falls.
Angiosarcoma of the liver had been tentatively diagnosed in a resident
of the area adjacent to the chemical plants, prompting the present survey.
The resident lived on 57th street, two streets to the southeast of the Good-
year Chemical Plant. There was no known occupational exposure to vinyl
chloride, but the person lived at this address for some 50 or more years.
Ambient air samples were taken in the residential areas near the
chemical plants, in areas around the chemical complex, and in the areas of
downtown Niagara Falls to determine the concentration of vinyl chloride
in the atmosphere. Figure 1 shows all of the sites in Niagara Falls from
which ambient air samples were taken.
Three suspected cases of angiosarcoma of the liver were also reported
in the Buffalo area. Spot samples of ambient air in the residential neigh-
borhoods of each of these patients were taken for vinyl chloride analysis.
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CITY OF NIAGARA FALLS
Figure 1. Locations of sampling sites for vinyl chloride measurements in Niagara Falls.
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EXPERIMENTAL
Time-integrated ambient air samples at the 57th Street residence
(Sampling Site No. 1) were collected in 300-liter Tedlar bags using a
stainless steel diaphragm pump over a period of 4 to 12 hours. From
the 300-liter bags containing the collected time-integrated samples,
20 to 25 liters of the sample were transferred into smaller Tedlar bags.
Ambient air grab samples of 20 to 30 liters were collected over 10- to
30-minute periods in small Tedlar bags using a 1-liter syringe as a
hand-operated pump. Care was taken not to unduly expose the bags to
sunlight after collection of the samples. Previous laboratory ex-
periments have shown Tedlar bags to be good sample containers for
Q
vinyl chloride air samples.
The collected air samples were flown to Houston, Texas, for
analysis of vinyl chloride by equipment being used there in an ambient
air study. Analysis of vinyl chloride was by gas chromatography with
flame ionization detection. One hundred milliliters of the air sample
were trapped in a 12-inch by 1/8-inch stainless steel column packed with
9
60/80 mesh glass beads at liquid nitrogen temperature. The liquid
nitrogen was removed and the trapped components were flushed into the
separating column consisting of a 12-foot by 1/8-inch stainless steel
column packed with 0.4 percent Carbowax 1500 on Carbopack A. The
3
helium carrier gas flow rate was 33 cm /minute. The column was main-
tained at 20 C during analysis. Conditioning of the column for 1
hour at 200 C was carried out before use in an effort to increase the
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separation of vinyl chloride from Freon-12. A calibration or response
factor for vinyl chloride was obtained by chromatographing known con-
centrations that were made up volumetrically and by plotting measured
peak area response from the chromatogrammed sample versus the concen-
tration of vinyl chloride. Vinyl chloride concentrations in the sam-
ples were calculated from measured response peak area multiplied by
the experimentally obtained response factor.
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RESULTS
The analytical results shown in Table 1 are of air samples collected
at Sampling Site No. 1, the 57th Street residence of the non-occupational case
of angiosarcoma of the liver. The highest concentration of vinyl chloride
was 40 parts per billion (ppb) measured from an air sample taken over a 5-hour
integrated period. During the early morning hours, the concentrations
of vinyl chloride were usually higher by a factor of two or more. With
wind direction from the north or north-northwest, there was greater pro-
bability of observing vinyl chloride in the residential area. In samples
taken when the wind direction was from the north or northwest, vinyl
chloride levels were below the detection limits of approximately 1.0
ppb. Also, the highs of 40 ppb and 9 ppb were observed when the wind
direction was north-northeast. It is not unreasonable that the wind
was at times from the northwest or other directions since only
generalized wind directions were obtained.
The data in Table 2 are for samples collected in the vicinity
of Goodyear Chemical (Sampling Sites 2 through 7). The samples from
Sites 2 and 6, obtained downwind of the plant, showed 3 ppb and 12.7
vinyl chloride, respectively. The sample from Site 7, collected
at the west side of the plant when the wind was from the north,
contained no vinyl chloride. This was to be expected since the
air parcel sampled had not come over the plant. Samples from Sites
3 through 5 were taken to show the dispersion and dilution effects
of vinyl chloride emissions downwind of a source. However, no
vinyl chloride was observed in any of the three samples. This
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Table 1. AMBIENT AIR SAMPLES FROM 57th STREET, NIAGARA FALLS
(Sampling Site No. 1)
Samples from
sampling
site no. 1
1
2
3
4
5
6
7
8
9
10
11
12
13
Remarks
8:00 p.m. to 8:00 a.m., 6/22, wind north-
northwest 10-17 mph.
8:00 p.m. to 8:00 a.m., 6/22, wind north-
northwest 10-17 mph (sample taken indoors
in the upstairs hallway).
12:00 midnight to 5:00 a.m., 6/24, wind
north-northeast 5/10 mph.
5:00 a.m. to 10:00 a.m., 6/24, wind north-
northeast 7-12 mph.
12:00 noon to 4:00 p.m., 6/24, wind north-
northeast 7-12 mph.
4:00 p.m. to 8:00 p.m., 6/24, wind north-
northeast 7-12 mph.
8:00 p.m. to 8:00 a.m., 6/24 - 6/25, wind
north 5-10 mph.
9:00 a.m. to 1:00 p.m., 6/25, wind north
5-10 mph.
1:00 p.m. to 6:00 p.m., 6/25, wind north-
northeast 5-12 mph.
7:00 p.m. to 1:00 a.m., 6/25 - 6/26, wind
north - northwest 5-10 mph.
1:00 a.m. to 9:00 a.m., 6/26, wind north-
northwest 5-10 mph.
10:00 a.m. to 2:00 p.m., 6/26, wind
northwest 5-10 mph.
2:00 p.m. to 6:00 p.m., 6/26, wind north-
northwest 5-10 mph.
Vinyl chloride
concentration, ppb
Oa
0
40
9
0
9
6.1
0
0
6.6
27.5
5.5
6.6
Below the detection limit of ~ 1.0 ppb.
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Table 2. AMBIENT AIR SAMPLES FROM VICINITY OF GOODYEAR CHEMICAL
(Sampling Sites No. 2 through 7)
Sampling
site no.
2
3
4
5
6
7
Remarks
4:00 p.m. to 4:15 p.m. ,
northwest 5-12 mph.
11:00 a.m. to 11 :10 a.m.
northeast 7-12 mph.
11:15 a.m. to 11:25 a.m.
northeast 7-12 mph.
12:00 a.m. to 12:30 p.m.
northeast 7-12 mph.
3:05 p.m. to 3:35 p.m. ,
northeast 5-10 mph.
10:00 a.m. to 11 :00 a.m.
5-10 mph.
6/21, wi
, 6/24,
, 6/24,
, 6/24,
nd north-
wind north-
wind north-
wind north-
6/25, wind north-
, 6/26,
wind north
Vinyl chloride
concentration, ppb
3
0
0
0
12.7
0
indicates either that emissions were low at the time or consid-
erably below the limit of detection.
Samples taken in or around the chemical complex contained vinyl
chloride in two of the five samples. The sample from Site No. 11
(Table 3), collected over 35 minutes downwind of the Goodyear Chem-
ical and Hooker Chemical plants, contained 28.6 ppb vinyl chloride.
The sample site was about 0.5 mile from Hooker Chemical and 1 mile
from Goodyear Chemical. The sample from Site No. 6 (Table 2), col-
lected 1 hour earlier at a location 1 mile downwind of Goodyear
Chemical, contained only 12.7 ppb vinyl chloride. It is difficult
to determine from these limited data if the higher value obtained
downwind of both plants was caused by emissions from both Good-
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Table 3. AMBIENT AIR SAMPLES FROM VICINITY OF CHEMICAL
CHEMICAL COMPLEX LOCATED ON BUFFALO ROAD
(Sampling Sites No. 8 through 12)
Sampling
site no.
8
9
10
11
12
Remarks
11:25 a.m. to 11:55 a.m., 6/24, wind north-
northeast 7-12 mph; sample taken while walk-
ing 3/4 mile distance on Buffalo Road.
11:15 p.m. to 1:30 p.m., 6/25, wind north-
northeast 5-10 mph
2:15 p.m. to 2:30 p.m., 6/25, wind north-
northeast 5-10 mph.
4:00 p.m. to 4:35 p.m., 6/25, wind north-
northeast 5-10 mph.
3:00 p.m. to 4:00 p.m., 6/25, wind northeast
5-10 mph; sample collected over 1.2-mile
distance along River Road.
Vinyl chlori
concentration,
0
0
0
28.6
2.5
de
ppb
year Chemical and Hooker Chemical or by an increase in emissions
from Goodyear Chemical. Hooker Chemical does produce halogenated
organics; vinyl chloride may or may not be one of them. However, no
vinyl chloride was detected in samples taken in close proximity of
the Hooker Chemical Plant (Sites 8, 9, and 10; Table 3).
Samples taken upwind of the chemical complex and in downtown
Niagara Falls (Table 4) showed no detectable vinyl chloride. An
indoor air sample taken in a downtown beauty shop (Site No. 15) fre-
quented by the 57th Street angiosarcoma case contained 3 ppm Freon-12.
At a concentration of 3 ppm Freon-12, 5 ppb of vinyl chloride could have
gone undetected, since chromatographic elution times of Freon-12
and vinyl chloride do not differ greatly. However, if vinyl chloride
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Table 4. AMBIENT AIR SAMPLES OUTSIDE NIAGARA FALLS INDUSTRIAL AREA
(Sampling Sites No. 13 through 15)
Sampling
site no.
Remarks
Vinyl chloride
concentration, ppb
13
14
15
10:40 a.m. to 11:00 a.m., 6/25, wind north-
northeast 5-12 mph.
11:50 a.m. to 12:10 p.m., 6/25, wind north-
northeast 5-12 mph; sample taken over three
block area of Main Street downtown Niagara
Falls area.
3:00 p.m. to 3:15 p.m., 6/21, beauty shop,
large room 30 ft by 30 ft well-ventilated.
Sample included a one-second burst of aero-
sol hair spray into the room. (Three ppm
Freon-12 was observed in sample.)
0
was present in Che beauty shop sample, its concentration was probably
much less than 1 ppm. Freons-11 and -12 are commonly used as pro-
pellants in aerosol spray cans; vinyl chloride has also been used as
a propellant.
Mo measurable amounts of vinyl chloride were found in the
three Buffalo air samples (Table 5) collected near the homes of the
other reported angiosarcoma cases. These samples were all collected
on one day within a 4-hour period. The three locations were in the
northwest and north-central section of Buffalo; no large chemical
plants were observed in the vicinity of these areas. The probability
of observing vinyl chloride from just three samples all taken within
A hours is small. More samples, particularly 12- or 24-hour time-in-
tegrated samples, would be necessary to determine conclusively if there
are any vinyl chloride emissions in the area.
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Table 5. AMBIENT AIR SAMPLES FROM BUFFALO AREA
Sample
no.
Remarks
Vinyl chloride
concentration, ppb
1 12:45 p.m. to 1:00 p.m., 6/25, wind north-
northeast 7-12 mph. in area of Dearborn Street.
2 1:10 p.m. to 1:30 p.m., 6/25, wind north-
northeast 7-12 mph, in area of Fargo Street.
3 3:30 p.m. to 4:00 p.m., 6/25, wind north-
northeast 7-12 mph, in area of Elmer Street.
0
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DISCUSSION AND CONCLUSIONS
Emissions of vinyl chloride to the ambient atmosphere at vinyl
chloride plants usually occur as leaks from valves, flanges, seals,
and pumps. Other losses occur in venting processes and in the opening
and purging of equipment in cleanup operations. Accidental release
of gas as a result of operator error or equipment failure occurs at times,
Vinyl chloride emissions can also result from unreactcd vinyl chloride
gas that is given off from polyvinyl chloride resins. At fabricating
plants the release of vinyl chloride may be facilitated by heating and
forming operations.
Vinyl chloride released either continuously or at intervals in the
above-mentioned ways is dispersed and diluted by air movements. Amounts
of vinyl chloride emitted and climatic conditions at the time of emis-
sions will dictate not only the concentrations to be found in the ambient
atmosphere, but also the areas in which highest concentrations will occur.
Many chemical plants in the area were producing or using chemicals
such as chlorine, halogenated organics, and inorganics that are emitted
into the atmosphere. Although analyses were not conducted to determine
concentrations of these various compounds, when samples were taken
downwind or between the chemical plants, one's eyes, nose, and throat
were irritated by the chlorine or by other compounds present.
People in the residential area near the chemical plants com-
plain of damage done to aluminum exposed to the atmosphere. Alu-
minum windows and doors are pitted, and aluminum screens are not
very durable; most people have replaced the eroded screens with
fiberglass or plastic screens. Paints on homes are somewhat affected;
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in one instance, a house painted green had slowly turned blue in color,
Iron guard rails along the road and telephone pole guide wires near
the chemical complex are badly corroded. Aluminum alloy lamp poles
on River Drive south of the chemical complex have corrosion on the
side facing the chemical plants.
Although the concentrations of vinyl chloride found were not in
the parts-per-million range, it is not known what past emissions
may have been, or if samples collected were all on days of low
emissions or atmospheric conditions favoring dispersal. It has
been estimated that up to 4 tons of vinyl chloride per year might be
emitted from the Goodyear Chemical Plant through various mentioned
losses. These data were obtained by EPA, Emission Standards and
Engineering Division, National Environmental Research Center, Re-
search Triangle Park, from a report submitted by the Goodyear Chem-
ical Company.
This survey indicates that residential areas adjacent to the
chemical complex in Niagara Falls are exposed to at least low levels
of vinyl chloride resulting from emissions by the chemical plants.
The residential areas to the east-southeast and west of the Good-
year Chemical Plant are more susceptible to emissions from the
plants because of the close proximity of each and the frequency
of wind direction from chemical plants to residential areas.
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REFERENCES
1. Creech, Jr., J.L., and M.N. Johnson. Angiosarcoma of the Liver
in the Manufacture of Polyvinyl Chloride. J. Occup. Med. 16:
150-151, 1974.
2. Tabershaw, I.R. and W.R. Gaffey. Mortality Study of Workers in the
Manufacture of Vinyl Chloride and Its Polymers. J. Occup. Med.
.16:509-516, 1974.
3. Munson, R.R., J.M. Peters, and M.N. Johnson. Proportional Mortality
Among Vinyl Chloride Workers. Lancet. 397-398, August 17, 1974.
4. Marsteller, H.J., W.K. Lelbach, R. Muller, and P. Gedigke. Unusual
Splenomegalic Liver Disease As Evidenced by Peritoneoscopy and
Guided Liver Biopsy Among Polyvinyl Chloride Production Workers.
(Presented at the Working Group, Toxicity of Vinyl Chloride-
Polyvinyl Chloride, New York Academy of Sciences, New York, May
10-11, 1974.)
5. Nicholson, W.J., E.G. Hammond, and I.J. Selikoff. Mortality Ex-
perience of a Cohort of Vinyl Chloride-Polyvinyl Chloride Workers.
(Presented at the Working Group, Toxicity of Vinyl Chloride - Poly-
vinyl Chloride, New York Academy of Sciences, New York, May 10-11,
1974.)
6. EPA Memo: From E.Z. Finfer, Senior Plan Advisor Air Branch, to
C. Simon, Director, Environmental Programs, EPA Region II (New York),
October 3, 1974.
7. Private Communication with Dr. Paul Brubaker, Special Studies Section,
Environmental Protection Agency, National Environmental Research Center,
Research Triangle Park, North Carolina, June 1974.
8. Unpublished Data, Lonneman, W.A. Environmental Protection Agency,
National Environmental Research Center, Research Triangle Park,
North Carolina, 1974.
9. Lonneman, W.A., S.L. Kopczynski, P.E. Darley, and F.D. Sutterfield.
Hydrocarbon Composition of Urban Air Pollution. Environmental Science
and Technology. 8^:229, 1974.
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TECHNICAL REPORT DATA
(Please read Inunctions on the reverie before completing/
1. REPORT NO.
EPA-650/4-75-020
3. RFCIPIF.NT'S.ACCESSION-NO.
4. TITLE AND SUBTITLE
Ambient Air Measurements of. Vinyl Chloride
In the Niagara Falls Area
5. REPORT DATE
May 1975
6. PERFORMING ORGANIZATION CODE
/. AUTMOR(S)
Bruce W. Gay, Jr., and Richard C. Noonan
8. PERFORMING ORGANIZATION REPORT NO.
9. PIRFOHMING ORGANIZATION NAME AND ADDRESS
Environmental Protection Agency
National Environmental Research Center
Chemistry and Physics Laboratory
Atmospheric Chemistry and Physics Branch
10. PROGRAM ELEMENT NO. IAAOOA
ROAP No. 21AKC
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
A 6-day survey was conducted in the Niagara Falls area to determine the
concentration of vinyl chloride in the atmosphere. Samples were obtained in
a residential area adjacent to the chemical plants where vinyl chloride
emissions were suspected, in areas around the plants, and in other areas
of Niagara Falls. The highest concentration of vinyl chloride measured
was 40 ppb for a 5-hour integrated sample observed at a residential area
two blocks east of a vinyl chloride polymerization plant. Grab samples
taken downwind of chemical plants exhibited a high of 28 ppb. Samples
taken from downtown Niagara Falls and upwind north of the chemical plants
contained no detectable vinyl chloride. The areas surrounding the chemical
plants, including the adjacent residential areas, are also affected by
emissions into the atmosphere of chlorine and other halogenated compounds
as exhibited by the deterioration of metal surfaces,particularly aluminum
windows and doors.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Vinyl Chloride
Air analysis
Chlorine and Halogenated Compounds
I). IDENTIFIERS/OPEN ENDED TERMS C. COSATI llcM/Croup
1B. DISTRIBUTION STATEMENT
Release Unlimited
19. SECURITY CLASS (This Report)
None
21. NO. OF PAGES
20
20. SECURITY CLASS (Tttispoge)
None
22. PRICE
EPA Form 2220-1 (9-73)
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