EPA 560/6-76-002
SAMPLING AND ANALYSIS OF SELECTED TOXIC SUBSTANCES
Task III - Vinyl Chloride, Secondary Sources
Environmental Protection Agency
Office of Toxic Substances
Washington, D.C. 20460
April, 1976
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EPA-560/6-76-002
SAMPLING AND ANALYSIS OF SELECTED TOXIC SUBSTANCES
Task III - Vinyl Chloride, Secondary Sources
Contract No. 68-01-2646
Project Officer
William A. Coniglio
Office of Toxic Substances
Environmental Protection Agency
Washington, D.C. 20460
Prepared for
Environmental Protection Agency
Office of Toxic Substances
Washington, D.C. 20460
April 1976
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NOTICE
This report has been reviewed by the Office of Toxic Substances, Environ-
mental Protection Agency, and approved for publication. Approval does not
signify that the contents necessarily reflect the views and policies of
the Environmental Protection Agency. Mention of tradenames or commercial
products is for purposes of clarity only and does not constitute endorse-
ment or recommendation for use.
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CONTENTS
Sections Page
I Summary and Conclusions 1
II Introduction . . 2
III Screening and Selection of Sampling Environments .... 3
Vehicles 4
Commercial Products 4
IV Discussion of Sampling Environments 6
Vehicles 6
Commercial Products 9
V Development of Sampling and Analysis Protocol 12
Method Development and Evaluation 12
Preparation of Charcoal Adsorption Tubes 12
Sample Collection and Storage 13
Removal of Vinyl Chloride from Charcoal with Carbon
Disulfide 14
Gas Chromatographic Analysis 14
Adopted Protocol 17
Equipment 17
Sampling Procedure 19
Analysis Procedure . 19
VI Results and Discussion 20
Vehicles 20
Commercial Products 20
References 26
11
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FIGURES
. Title Page
1 Location of Nursery Equipment. 11
2 Chromatograms from Latex-Painted Room - Column 1 23
3 Chromatograms from Latex-Painted Room - Column 2 24
TABLES
No. Title Page
1 Sampling Data 7
2 Effect of Storage Time on Recovery of Vinyl Chloride 15
3 Recovery of Vinyl Chloride at Different Loadings 16
4 Gas Chromatographic Conditions 16
5 Relative Retention Times . . . 18
6 Results of Vinyl Chloride Analysis 21
111
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SECTION I
SUMMARY AND CONCLUSIONS
A sampling and analysis program was conducted to determine whether
and to what extent vinyl chloride was present in ambient air due to the
presence of polyvinyl chloride products. Sampling environments were chosen
to represent real life, but nonwork situations where a significant expo-
sure to polyvinyl chloride products might occur.
The air samples were collected by drawing a known volume of air
through a tube of activated charcoal. The trapped vinyl chloride was de-
sorbed by carbon disulfide at dry ice temperature. The overall trapping
and desorption efficiency was generally greater than 90%. The carbon
disulfide extracts were analyzed for vinyl chloride by gas chromatography
using flame ionization detection. Two different columns were routinely
employed to confirm identity. With the sampling and analysis protocol
normally employed, the detection limit was 10 ppb (v/v).
The two general categories of environments sampled were vehicles
and commercial products. The interior ambient air of the following ve-
hicles were sampled: Chevrolets—1976, 1975; Ford—1976, 1975, 1974;
Plymouth—1976, 1975, 1974; AMC—1976, 1975, 1974; Volkswagen—1976,
1975, 1974; Toyota—1976, 1975; Skyline mobile home-new and used; and
Champion mobile home—new and used. No evidence of vinyl chloride was
found. The following commercial vinyl products, when sampled in their
normal environment, did not produce a measurable quantity of vinyl
chloride in the ambient air: vinyl wall covering; vinyl swimming pool
liners; and vinyl nursery products—mattress pad, bumper pads, changing
table pad, playpen pad, and toy box. Samples of vinyl shower curtains
and pull shades, confined in a small sealed chamber, did not release
measurable levels of vinyl chloride. A 12 x 10 x 12 ft room painted with
ca 3-1/2 gal. of Tomato Red paint, obtained from Cook Paint Company, was
found to contain a small but measurable level of vinyl chloride. The
levels were in ppb (v/v): 22 during painting, 4 during and after paint-
ing, and not detectable 1 day later.
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SECTION II
INTRODUCTION
The objective of this program is to provide the Environmental Pro-
tection Agency with sampling and analysis capabilities to determine the
levels of toxic substances in air, water, soil, and other miscellaneous
samples from designated sources and ambient locations throughout the
United States. The toxic substance studied in this task was vinyl chlo-
ride.
The origin of this task was the Vinyl Chloride Task Force Recommen-
dation No. 4--"A program should be initiated to determine whether and
to what extent background levels of vinyl chloride are present in the
ambient air--indoors and outdoors--due to the presence of polyvinyl
chloride products." This report contains a discussion of the selection
of sampling environments, the development of a sampling and analysis
protocol, and the presentation and discussion of the results for vehicles
and commercial products.
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SECTION III
SCREENING AND SELECTION OF SAMPLING ENVIRONMENTS
The task called for the selection of sites or environments at which
an exposure to vinyl chloride existed due to the presence of polyvinyl
chloride products. The following environments were specified:
A. Vehicles
1. Domestic automobiles;
2. Foreign automobiles;
3. Mobile homes; and
4. Recreational vehicles.
B. Commercial products
1. Latex paint;
2. Vinyl wall covering;
3. Vinyl fabric; and
4. Nursery equipment.
In all cases, duplicate samples were to be collected for analysis.
The principle criteria in site selection was that the environment
be in a real life but nonwork place situation. In all instances, coopera-
tion of the appropriate dealer or user of a product was obtained prior
to sampling. Additional criteria were imposed with the selection of spe-
cific environments.
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VEHICLES
Whenever possible, sampling was conducted on a relatively warm day
between 10:00 a.m. and 4:00 p.m. Vehicles were chosen, if available, that
had dark exterior and interior finishes. In all instances, the vehicles
were on the sales lot and were not running.
Domestic Automobiles
A 1976 compact or family sized passenger vehicle was selected from
the Ford, Chevrolet, Plymouth, and AMC lines. Comparable 1975 and 1974
models were also sampled when they were available.
Foreign Automobiles
One 1976 top selling passenger vehicle was chosen from the Datsun,
Toyota, and Volkswagen lines. Comparable 1975 and 1974 models were also
sampled when available.
Mobile Homes
One new and one used mobile home each were chosen from,the Skyline
and the Champion lines. The vehicles sampled all had white exteriors.
Recreational Vehicles
Models were chosen from the best-selling lines of self contained
motor homes, trailer-type campers, and slide-in campers. All vehicles
were produced by Fleetwood Enterprises, Inc.
COMMERCIAL PRODUCTS
Generally sampling was conducted during real-life situations. Oc-
casionally, products were analyzed in the laboratory under severe condi-
tions to determine if any potential existed for vinyl chloride emission.
Latex Paint
The base of latex paint is an organic homo- or heteropolymer. Common
polymers used for interior or exterior paints have been polyvinyl acetate,
polyacrylates, or copolymers of vinyl acetate and acrylate. Five paint
companies surveyed in the preparation of this report, Benjamin Moore,
Pratt and Lambert, Colony Paint, Great Western, and Davis, stated that
no polyvinyl chloride is used in the formulation of their paints. Cook
Paint Company reported that a terpolymer of vinyl chloride, vinyl ace-
tate, and ethylene is used in a minor portion of their line. The terpoly-
mer, obtained as Airflex 728 from Air Products and Chemicals, is used in
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the formulation of what is termed Accent paints. These are paints which
are highly pigmented, with deep or dark colors. Since the probability of
finding a real-life use of these specific paints was quite low, a room
at MRI was selected for painting with this paint.
Vinyl Wall Covering
A retail wall covering outlet having an appreciable display stock
was desired for sampling. The site that was chosen, Dwoskins, maintained
a large display stock and a significant warehouse stock, and both areas
were sampled. An environment in which vinyl wall coverings were being
installed was also desired. For reasons discussed later, this environ-
ment was not sampled.
Vinyl Fabric
An environment was desired in which commercial vinyl fabrics such
as shower curtains or vinyl window shades were to be installed. For rea-
sons discussed later, these products were analyzed in the laboratory and
no real-life situations were tested. Also, a retail outlet carrying an
appreciable stock of vinyl products was sampled. The outlet chosen sold
vinyl swimming pool liners.
Nursery Equipment
An environment was desired in which new nursery equipment was to
be installed. The newly equipped nursery of an expectant MRI employee
was chosen for sampling.
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SECTION IV
DISCUSSION OF SAMPLING ENVIRONMENTS
Details of each sampling environment are described below. When ap-
propriate, diagrams showing the location of potential sources, samplers,
etc., are presented.
VEHICLES
Domestic Automobiles
The domestic automobiles were sampled at the following locations:
AMC, Friendly AMC, 7712 Wornall, Kansas City, Missouri; Chevrolet, Pappas
Chevrolet, 115 West Gregory, Kansas City, Missouri; Ford, Southtown Ford,
1326 East 47th, Kansas City, Missouri; Plymouth, Downtown Plymouth, 8625
Troost, Kansas City, Missouri. The sampling equipment was placed inside
the vehicle with an on/off switch for the pump placed outside the vehicle.
The charcoal adsorption tubes were situated at head height midway between
the driver and the front seat passenger. After installation of the sampling
equipment, a period of 30 min was allowed to pass before collecting air
samples. Table 1 summarizes the relevant data collected at the time of
sampling.
Foreign Automobiles
The foreign automobiles were sampled at the following locations:
Toyota, Toyota of Kansas City, Inc., 1325 Bannister Road, Kansas City,
Missouri; and Volkswagen, Bunker Volkswagen, Inc., 7800 Wornall, Kansas
City, Missouri. The location and operation of the sampling equipment was
identical to that of the Domestic Automobiles. Relevant data pertaining
to the sampling is summarized in Table 1.
Mobile Homes
The mobile homes were sampled at the following locations: Champion,
K and H Mobile Homes, St. Joseph, Missouri; and Skyline, Pitts Mobile
Homes, 8747 East 40 Highway. Sampling stations were located in the bed-
room, the living room, and the kitchen at a height of 4 ft. The units
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Table 1. SAMPLING DATA
Environment or site location
Date
Times
Volume
sampled
Temperature (I.)
Vehicles
Domestic automobiles
Chevrolet
1976 Malibu station wagon, red with
with brown interior
1975 Impala, brown with brown
interior
10/10/75 1315-1345 Air - 31°C 2.65, 3.23
Seat - 29°C
10/10/75 1505-1535 Air - 35°C 3.29, 3.35
Seat - 32°C
Ford
1976 Gran Torino, blue with blue 10/11/75
interior
1975 Gran Torino, brown with brown 10/11/75
interior
1974 Gran Torino, brown with brown 10/11/75
interior
1325-1355 Air - 39°C 3.15, 3.44
Seat - 42°C
1205-1235 Air - 43°C 3.60, 3.90
Seat - 45°C
1445-1515 Air - 32°C 3.08, 3.09
Seat - 29°C
Plymouth-Chrysler
1976 Valiant, black with black 10/13/75
interior
1975 Duster, tan with tan interior 10/13/75
1974 Duster, metallic brown with 10/13/75
brown interior
1200-1230 Air - 24°C 3.48, 3.66
Seat - 20°C
1330-1400 Air - 26°C 2.27, 4.50
Seat - 23°C
1445-1515 Air - 25°C 3.23, 3.68
Seat - 25°C
AMC
1976 Hornet, tan with brown 11/17/75
interior ,
1975 Hornet, tan with brown 11/17/75
interior
1974 Matador, black with black 11/17/75
interior
1245-1315 Air - 33°c 2>25> 4'29
Seat - 32°C
1435-1505 Air - 30°C 3.05, 3.63
Seat - 34°C
1400-1430 Air - 29°C 2.63, 3.30
Seat - 27°C
Foreign automobiles
Volkswagen
1976 Rabbit,, green with tan 11/18/75
interior
1975 Rabbit, green with black 11/18/75
interior
1974 Beetle, gold with brown 11/18/75
interior
1430-1500 Air - 27°C 1.55, 3.00
Seat - 26°C
1315-1345 Air - 29°C 2.66, 3.15
Seat - 26°C
1130-1200 Air - 28°C 3.11, 3.34
Seat - 25°C
Toyota
1976 Corolla, red with black 11/19/75
interior
1975 Corona, gray with black 11/19/75
interior
1120-1150 Air - 21°C 2.25, 3.19
Seat - 20°C
1310-1340 Air - 24°C 3.19, 3.20
Seat - 24°C
Mobile homes
Skyline
New, 70 x 14 ft, two bedroom, white 11/6/75
Far bedroom
Living room
Kitchen
Used (1970), 70 x 14 ft, two 11/6/75
bedroom, white
Far bedroom
Living room
Kitchen
1045-1115 Air - 20°C 0.58, 3.03
1130-1200 Air - 20°C 2.43, 2.68
1220-1250 Air - 20°C 2.01, 3.70
1450-1525 Air - 22°C 2.92, 4.20
1535-1605 Air - 22°C 2.73, 4.69
1610-1640 Air - 22°C 3.35, 4.02
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Table 1. (concluded)
Environment or site location
Date
Times
Temperature
Volume
sampled
Champion
New, 70 x 14 ft, two bedroom, white
Far bedroom
Living room
Kitchen
Used, 60 x 12 ft, two bedroom,
white
Far bedroom
Living room
Kitchen
Commercial products
Latex paint
Test room, 12 x 10 x 12 ft, painted
0900-1200, 1300-1500 on 12/9/75
Vinyl wall covering
Warehouse
Showroom
Vinyl fabrics
Swimming pool lines, single large
pool
Swimming pool lines, two small
pools
Nursery equipment
Crib corner
Crib center
Changing table
Toy box
Crib corner
Crib center
Changing table
Toy box
Playpen pad
11/11/75
11/11/75
12/9/75
12/9/75
12/10/75
11/25/75
11/25/75
11/25/75
12/2/75
12/2/75
12/2/75
12/2/75
12/3/75
12/3/75
12/3/75
12/3/75
12/22/75
1100-1130
1135-1205
1210-1240
1315-1345
1400-1430
1440-1510
1130-1200
1300-1700
0900-1300
1005-1035
1110-1140
1415-1445
1510-1540
0900-0930
0940-1010
1030-1100
1115-1145
1020-1050
1055-1125
1145-1215
1230-1300
2000-2200
Air -
Air -
Air -
Air -
Air -
Air -
Air -
Air -
Air -
Air -
Air -
Air -
Air -
Air -
Air -
Air -
Air -
Air -
Air -
Air -
7°C
7°C
7°C
8°C
8°C
8°C
23°C
22°C
18°C
23°C
19°C
28°C
28°C
28°C
28°C
27°C
27°C
27°C
27°C
26°C
2.60,
3.15,
2.81,
2.95,
3.14,
2.82,
0.73,
17
39
1.34,
2.28,
1.64,
1.79,
1.37,
1.49,
1.70,
3.88,
1.62,
1.54,
2.11,
1.68,
10.12
4.86
3.27
4.56
5.18
5.81
7.56
2.69
.55
.60
2.21
3.00
3.57
4.27
2.16
3.66
4.33
4.68
2.58
2.54
2.63
3.73
, 10. i
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were closed for at least 30 min before air samples were collected. Table
1 summarizes the relevant data collected at the time of sampling.
Recreational Vehicles
No samples were collected from recreational vehicles for several
reasons. No vinyl chloride had been detected in any of the automobiles
or mobile homes that had been sampled. Furthermore, the ambient temper-
ature had dropped to ca 0 C which would decrease the possibility of vinyl
chloride emission.
COMMERCIAL PRODUCTS
Latex Paint
An unoccupied room at MRI, removed from the laboratory areas, was
used for testing latex paint. The room was 12 x 10 x 12 ft with normal
ventilation. During painting and sampling, the door was kept closed. The
sampler was positioned 1 m from the wall at a height of 1 m. Two coats
of paint were applied between 0900 and 1500; however, no painting was
done between 1200 and 1300. Approximately 3-1/2 gal. of paint was applied.
The paint was Tomato Red, Code 002, obtained from the Cook Paint Company,
Kansas City, Missouri. As a precaution, the painter was required to wear
a carbon filter mask while painting. Sampling data are summarized in Table
1.
Vinyl Wall Covering
Air samples were collected from the showroom and the warehouse at
Dwoskin, 10770 El Monte, Kansas City, Kansas. One sample station was po-
sitioned in the showroom next to a display of vinyl wall coverings. The
second sampler was positioned in the center of the 20 x 40 m warehouse
containing a large supply of rolled wall coverings. A strong odor was
present at both locations. Sampling data are summarized in Table 1.
A'sample of vinyl wallpaper paste was tested for vinyl chloride by
placing 6 g in a 7.5 ml vial fitted with a septum. After 1 hr at ambient
temperature, head space air samples were removed for analysis using gas
tight syringes. The vial was heated to 60 C for 1 hr and the test repeated.
Vinyl Fabrics
An air sample from a vinyl fabric environment was collected at the
Esther Williams Pool Company, 6231 Troost, Kansas City, Missouri. Three
swimming pool liners were on display in a showroom. The pools were circu-
lar with diameters of approximately 10.5 and 5 m and depths of 1 m. Air
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samples were collected immediately adjacent to the pools. Sampling data
are summarized in Table 1.
Other- vinyl fabrics sampled were a vinyl shower curtain and a vinyl
pull shade. Both were purchased from a local T.G.&Y. store. The shower
curtain was gold print and carried the name Drapecraft. The white pull
shade was manufactured by Clopay Corporation, Cincinnati, Ohio.
In both cases, initial screening experiments were performed by plac-
ing the product in a closed chamber and sampling the head space. A por-
tion of the vinyl window shade 86 x 90 cm, weighing 117 g (approximately
30% of the curtain), was placed in a 1.0 liter screw-top jar fitted with
a septum. Air samples were collected by gas tight syringe periodically
for up to 2 hr at ambient temperature. The jar was also heated to 60 C
for 1/2 hr and air samples collected with a gas-tight syringe.
A 37 x 177 cm portion of vinyl shower curtain, weighing 92.8 g (ap-
proximately 20% of the shade), was placed in a 1.0 liter jar equipped
with a septum. With the jar at ambient temperature, air samples were re-
moved with an air-tight syringe and analyzed periodically for 2 hr. The
jar was then heated to 60°C for 1/2 hr and air samples analyzed as before.
Nursery Equipment
The nursery equipment was located in a 10 x 11 ft room arranged as
shown in Figure 1. The following new items were installed in the room
immediately before sampling was begun.
1. Vinyl mattress coverJ
2. Vinyl covered bumper pads;
3. Vinyl covered wastebasket;
4. Vinyl covered toy chest;
5. Assortment of plastic toys;
6. Vinyl covered changing table pad; and
7. Vinyl diaper bag.
Samples were collected at the center and at a corner of the crib,
at the surface of the changing table, and adjacent to the toy chest, toys
and vinyl wastebasket. A new playpen pad was installed in a playpen, and
air samples were collected at its center. Sampling data are summarized
in Table 1.
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Window
Wasiebasket
Diaper Bag
Crib
Changing Table
Placement of Sampling Tubes
Figure 1. Location of nursery equipment
N
Door
11
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SECTION V
DEVELOPMENT OF SAMPLING AND ANALYSIS PROTOCOL
METHOD DEVELOPMENT AND EVALUATION
The generally accepted procedure for determining vinyl chloride in
air utilizes the trapping of vinyl chloride on activated charcoal fol-
lowed by its desorption from charcoal using carbon disulfide. A well-
defined protocol is necessary to maintain acceptable recovery and pre-
cision. It is customary and highly advisable that each laboratory
conducting vinyl chloride analyses thoroughly evaluate their protocol
and establish overall recovery values. The critical steps which were
evaluated separately in this study were: (a) preparation of charcoal
adsorption tubes; (b) efficiency of collection; (c) stability of the
collected samples; and (d) desorption efficiency of carbon disulfide.
PREPARATION OF CHARCOAL ADSORPTION TUBES
As charcoal is a well-known adsorbent of organic vapor, it was neces-
sary to be able to prepare a charcoal which was free of any organic mate-
rial which could interfere with the analysis.
Coconut charcoal, 6 to 14 mesh, obtained from Fisher Chemical, was
heated to 250 C for 2 hr in a stream of purified nitrogen. After cooling,
the charcoal was transferred to a glass jar and bathed with nitrogen be-
fore capping. Stainless steel tubes, 3 x 1/4 in., were packed with about
400 mg charcoal and plugged with glass wool at both ends. Care was taken
to leave space at one end which was then marked Inlet. The ends were cov-
ered with precleaned aluminum foil and plastic caps, and the tubes were
stored in a closed jar under nitrogen. Prior to use, the individual tubes
were heated in an oven at 275 C for 15 min under nitrogen. Tubes prepared
in this fashion showed no peaks near the retention volume of vinyl chlo-
ride at maximum sensitivity.
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SAMPLE COLLECTION AND STORAGE
Sampling
Experiments were performed to determine the collection efficiency
and the breakthrough point of the charcoal tubes for vinyl chloride. A
stream of 10 ppm vinyl chloride in nitrogen was sampled continuously
through two charcoal traps in series. The stream was sampled at 100 ml/
min. The vinyl chloride was generated by calibrated permeation tubes.
After 255 min, the traps were removed and immediately analyzed for vinyl
chloride. More than 99.7% of the total vinyl chloride trapped was found
on the first tube. The adopted sampling protocol was designated as 30
to 120 min with the capability of extension to 240 min if desired. Air
samples were collected using the train shown below.
Needle Valve
Charcoal Tube
Air was pulled through the tube at 100 ml/min for a given time. Flow
rates were controlled by a needle valve and checked at the beginning, the
midpoint, and at the end of the sampling period.
Storage
Once the charcoal tubes are used to collect vinyl chloride, it is
necessary to know if they are stable and how long they can be stored
prior to analysis.
A series of charcoal tubes were loaded by sampling 4 ppm nitrogen
at 100 ml/min for 10 min. The tubes were capped and stored in crushed
dry ice until analyzed. The tubes were analyzed periodically for up to
7 days after collection. Recoveries were high as expected within the first
24 hr. Tubes stored longer than that began to show low recoveries. Since
all the tubes were prepared at the same time in an identical fashion, the
drop in recovery must be related to storage time.
An experiment was devised to test for loss of vinyl chloride by vola-
tilization. It was felt that the most serious loss would occur at the in-
let end of the tube since that is where the majority of the adsorbed vinyl
chloride is trapped. Vinyl chloride migrating down the tube, toward the
outlet would be readsorbed by the charcoal. Vinyl chloride diffusing to-
ward the inlet end, however, would not be readsorbed and could be lost.
Tubes were loaded with vinyl chloride by collecting a gas sample from
the permeation tube. Approximately 50 mg of charcoal was immediately
added to the inlet end of the tube and the tube was plugged with glass
wool. After recapping, the tubes were stored in dry ice until analyzed.
13
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The results are summarized in Table 2. Tubes analyzed with 24 hr
after collection generally gave acceptable recoveries without supplemen-
tary charcoal. Beyond 1 day, recoveries were low and variable. The tubes
prepared with supplementary charcoal gave high recoveries for up to 5
days after collection. As expected, a significant fraction of the vinyl
chloride was present on the added charcoal.
REMOVAL OF VINYL CHLORIDE FROM CHARCOAL WITH CARBON BISULFIDE
The trapped vinyl chloride is readily extracted from charcoal with
carbon disulfide. The reaction of charcoal and carbon disulfide, however,
is highly exothermic and localized boiling can occur. Due to the high
volatility of vinyl chloride, care is necessary in this step to avoid its
loss. It is necessary to establish both the time required for complete
desorption and the efficiency of desorption.
Vials with a 3.5 ml capacity were fitted with Rubber-Teflon® lamin-
ated discs (Teflon® side down) and open top screw caps. The vials were
set in crushed dry ice and 2 ml carbon disulfide were added. All of the
charcoal from the adsorption tubes was slowly added to the cooled vial.
The glass wool plugs were discarded. The cap was replaced and the vial
was left in the dry ice. At various intervals, a 5 ^1 sample was with-
drawn and analyzed. Recovery was constant from 25 to 140 min after mix-
ing. In the adopted protocol, a 30 min waiting time was used.
The total recovery for nine tubes loaded with 11 to 13 Hg vinyl
chloride, and analyzed by the recommended protocol, averaged 96.6% with
an estimated standard deviation of 7.3%. A measure of percent recovery
at very low loadings was also made, and the results are reported in
Table 3.
GAS CHROMATOGRAPHIC ANALYSIS
Vinyl chloride was analyzed by gas chromatography using hydrogen
flame ionization detection. Two columns were used for separation and
confirmation of identity. The first column (Column 1) was 6 ft x 1/8
in. stainless steel, packed with 80/100 mesh Chromosorb 102, followed
by 6 ft x 1/8 in. stainless steel, packed with 10% DO200 on 100/120
Supelcoport. The second column (Column 2) was 6 ft x 1/8 in. stainless
steel, packed with 0.4% Carbowax 1500 on Carbopak A. Operating conditions
and temperatures are summarized in Table 4.
Calibration curves were prepared by injecting 0.050 to 1.00 ml
samples of vinyl chloride in nitrogen. The gas samples were obtained
from a calibrated permeation tube apparatus that was adjusted to pro-
vide a stream of nitrogen containing from 0.6 to 100 ppm (v/v) vinyl
chloride. Calibration curves ranged from 0.25 to 9.85 ng/injection and
were linear. A reasonable limit of detection was 0.1 ng.
14
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Table 2. EFFECT OF STORAGE TIME ON RECOVERY OF VINYL CHLORIDE
I. Percent recovery - no additional charcoal
Run No. Time before analysis % Recovery
1 1 to 4 hr 93, 103, 80, 90, 86, 90
2 24 hr 97, 93, 54
3 ' 2 to 7 days 53, 44, 71, 87, 63
II. Percent recovery - charcoal added to inlet
Run No. Time before analysis % Inlet % Main Total % recovery
4 2 to 4 hr 1.4 87.8 89.2
5 2 to 4 hr 2.3 97.7 100.0
6 2 to 4 hr 4.1 90.1 94.2
7 24 hr 10.5 97.5 108.0
8 24 hr 14.6 76.2 90.8
9 24 hr 10.4 97.0 107.4
10 5 days 9.9 81.7 91.6
11 5 days 15.4 83.3 98.7
12 5 days 9.2 80.5 89.7
15
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Table 3. RECOVERY OF VINYL CHLORIDE AT DIFFERENT LOADINGS
Nanograms sampled Nanograms found % Recovery
11,000-13,000 96.6
768 603 79
384 247 64
230 134 58
154 112 73
Table 4. GAS CHROMATOGRAPH1C CONDITIONS
Column 1 Column 2
Column temperature 150°C Ambient
Injector temperature 210°C 180°C
Detector temperature 210°C 210°C
Retention time 2.0 min 1,3 min
16
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A series of low molecular weight hydrocarbons were tested as po-
tential interferants for vinyl chloride. Retention times, relative to
vinyl chloride, were determined and are listed in Table 5. The data for
Column 1 was actually obtained at 100°C for Chromosorb 102 alone. At
150 C, acetaldehyde and vinyl chloride coelute on the prescribed column
and are indistinguisable. Since all the samples were first analyzed on
Column 1 at 150 C, the presence of a peak at the retention time of vinyl
chloride may be due to acetaldehyde. Accordingly, Column 2 was used for
further identification. As indicated in Table 5, vinyl chloride and
acetaldehyde are well resolved on this column.
ADOPTED PROTOCOL
This section describes the equipment, sampling procedure, and analy-
sis procedure used for the determination of vinyl chloride.
EQUIPMENT
The following equipment is required for the sampling and analysis
for vinyl chloride:
Charcoal, coconut, 6 to 14 mesh, Fisher Chemical
Stainless steel tubes, 3 x 1/4 in.
Air sampling pump with 1 liter/min capacity
Rotameter, 0 to 200 ml/min
3.5 ml Glass vials
Rubber-Teflon® laminated discs
Open top screw caps
Flame ionization gas chromatograph
Column: (1) 6 ft x 1/8 in. stainless steel packed with 80/100 Chromo-
sorb 102 coupled to 6 ft x 1/8 in. stainless steel packed
with 10% DO200 on 100/120 Supelcoportj (2) 6 ft x 1/8
in. stainless steel packed with 0.4% Carbowax 1500 on
Carbopak A
10 |j,l Syringe
Carbon disulfide
Dry ice
17
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Table 5. RELATIVE RETENTION TIMES
Compound
Methane
Ethane
Ethylene
Propane
Methyl chloride
Acetaldehyde
Isobutane
Isobutylene
Methane 1
1-Butene
n-Butane
1,3-Butadiene
Trans-2-butene
Ethyl chloride
Cis-2-butene
1, 1-Dichloroethylene
aj 6 ft x 1/8 in. stainless
102 held at 100° C
b/ 6 ft x 1/8 in. stainless
Carbopak A at ambient
a/
Column 1—
0.15
0.21
0.21
0.54
0.63
0.93-
1.22
1.37
-
1.43
1.57
1.57
1.57
1.70
1.73
2.00
steel packed with
steel packed with
temperature
c/ Acetaldehyde and vinyl chloride coelute at
b/
Column 2—
0.20
0.29
0.26
0.63
0.45
0.77
-
-
1.38
.
1.83
-
2.92
1.54
-
-
80/100 mesh Chromosorb
0.4% Carbowax 1500 on
150°C
18
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SAMPLING PROCEDURE
The necessary number of charcoal tubes are prepared using the pro-
cedure outlined previously. The sealed tubes are stored in a closed glass
jar until used. Air samples are collected at a rate of 100 ml/min for
exactly 30 min. By the use of a calibrated rotameter, the flow rates are
measured after 1, 15, and 29 min. The temperature is recorded before and
after collecting the sample. Approximately 50 mg of charcoal are added
to the inlet end of the tube and the tube plugged with a small portion
of glass wool. Both ends of the tube are covered with aluminum foil and
capped. The tube is then wrapped in aluminum foil and stored in crushed
dry ice. A blank is taken to the field and treated in the same manner
except that no air is drawn through it.
ANALYSIS PROCEDURE
Vials with a 3.5 ml capacity are fitted with TefIon®-laminated septa
and open-top screw caps. Exactly 2.0 ml carbon disulfide is added and
the vials are placed in crushed dry ice. The glass wool plug is removed
from the inlet end of the tube and the supplementary charcoal is added
to the vial. The next glass wool plug is removed and the remaining char-
coal is added. The vial is immediately capped, swirled to mix, and left
in the dry ice for 30 min. A 5 M<1 portion of the carbon disulfide is in-
jected onto the Chromosorb 102/DO200 column held at 150° C. The next sam-
ple is injected as soon as a stable baseline is achieved. A calibration
curve of peak height versus nanograms injected is prepared by analyzing
standards prepared appropriately. The quantity of vinyl chloride in the
carbon disulfide is calculated from observed peak height using the cali-
bration curve. From the volume of air collected, the concentration in
nanograms per liter or micrograms per liter is calculated. The results
are converted to parts per billion or parts per million, respectively,
by multiplying by 0.392. A recovery correction is made by multiplying
the results by 1.04.
Samples believed to contain vinyl chloride are analyzed on a second
column of Carbowax 1500 on Carbopak A to confirm identity.
19
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SECTION VI
RESULTS AND DISCUSSION
Table 6 summarizes the results obtained for the air samples collected
from the environments discussed previously. The results are presented as
an observed level or as ND (not detected). The level of 10 ppb (v/v) was
determined as the detection limit based upon normal protocol and was
established in the following manner. It was assumed that the air sample
collected was 3 liters, that 2 ml of carbon disulfide was used for de-
sorption, and that 5 ^1 were injected. Setting a lower limit of absolute
detection of 0.2 ng/injection, it was calculated that the air sample must
be 10 ppb or greater. As reported in Table 6, no vinyl chloride was ob-
served at or greater than 10 ppb except in the room painting environment.
Samples as large as 20 to 30 liters were collected from the room which
permitted lowering the detection limit to 1 ppb.
VEHICLES
Automobiles, Domestic and Foreign
There was no indication of vinyl chloride in any of the automobiles
sampled.
Mobile Homes
A peak was observed when using Column 1 for the samples collected
from the new Skyline mobile home. The samples were immediately analyzed
on Column 2 and no vinyl chloride peak was observed. It was concluded
that no vinyl chloride was present in the mobile homes above the detec-
tion limit.
COMMERCIAL PRODUCTS
Latex Paint
Latex paint may be formulated with a polymer in a water emulsion.
The organic polymer in later paints sold to the general public is gen-
erally a polyvinyl acetate, polyacrylate, or a copolymer of the two.
20
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Table 6. RESULTS OF VINYL CHLORIDE ANALYSIS
Sample
Chevrolet, 1976
1975
Ford, 1976
1975
1974
Plymouth, 1976
1975
1974
AMC, 1976
1975
1974
Volkswagen, 1976
1975
1974
Toyota, 1976
1975
Skyline, new
used
Champion, new
used
Latex paint
During
During and after
One day after
Vinyl wall covering
Warehouse
Showroom
Paste
Vinyl fabrics
Pool liners
Shower curtains
Pull shades
Nursery equipment
New crib corner
New crib center
New changing table
New toy box
New playpen pad
One day later - crib corner
One day later - crib center
One day later - changing table
One day later - toy box
Vinyl chloride, ppb (u/v)
a/
ND-
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
29,
NDfe/
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
a./ Unless otherwise noted, ND = not detected above 10 ppb (v/v).
b/ Detection limit of 1 ppb (v/v).
21
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Six major paint manufacturers in the Midwest were contacted in an at-
tempt to determine if polyvinyl chloride is used in paint formulation.
The following companies responded that they did not use polyvinyl chlo-
ride: Benjamin Moore, Pratt and Lambert, Colony Paint, Great Western,
and Davis. Cook Paint Company, 1412 Knox, Kansas City, Missouri, reported
a limited use of polyvinyl chloride in latex paint. A terpolymer of vinyl
chloride, vinyl acetate and ethylene is used in what is termed by Cook
Paint Company as accent colors. These paints are deeply colored and highly
pigmented. According to the company, this line of paints represents a
minor fraction of all latex paints. The terpolymer used by Cook Paint
Company is produced as Airflex 728 by Air Products and Chemicals.
Duplicate 30 min air samples were collected starting at 2-1/2 hr
after the painting began. The samples were first analyzed using Column
1. A peak was observed at the retention time of vinyl chloride as shown
in Figure 2. The samples were then analyzed on Column 2 to establish
whether vinyl chloride or acetaldehyde was being detected. As seen in
the chromatograms illustrated in Figure 3, peaks were observed both at
the retention time of vinyl chloride and acetaldehyde, thus confirming
their presence. A single 4-hr sample collected later the same day also
showed the presence of vinyl chloride and acetaldehyde. This sample was
collected during the last 2 hr of painting and for 2 hr after the paint-
ing was completed. A final set of 4 hr duplicate samples were collected
from 0900 to 1300 the following day and did not contain vinyl chloride.
The level of vinyl chloride for the three sampling periods was 22 ppb,
4 ppb, and not detected, respectively. The room had normal forced air
ventilation, and the decrease in vinyl chloride was as expected.
Vinyl Wall Covering
The air samples collected from the warehouse region, after analy-
sis on both columns, did not contain detectable levels of vinyl chloride.
The presence of acetaldehyde, however, was strongly indicated. The air
samples collected from the showroom contained neither vinyl chloride nor
acetaldehyde. Since no vinyl chloride was found in these environments,
it was decided to not sample a room being wall papered.
A sample of commercial ready-to-use vinyl wallpaper adhesive, pur-
chased from Montgomery Wards and Company, Inc., was tested for vinyl
chloride. A 6.0 g sample was placed in a 7.5 ml septum-equipped vial
and heated to 60°C for 30 min. The head space was sampled by a gas-tight
syringe and did not contain vinyl chloride.
22
-------
*
o
I
O
*
o
(b)
(c)
VC = Vinyl Chloride
AA = Acetaldehyde
k
o
I
o
(e)
(f)
(a) Sample collected during painting
(b) Duplicate
(c) Sample collected during and after painting
(d) Sample collected 24 hr later
(e) Blank
(f) Standard, 0.45 ng
Figure 2. Chromatograms from latex-painted room - Column 1
23
-------
(a)
0 (b)
I
(c)
U
U (d) U (e) " (0
VC = Vinyl Chloride
AA = Acetaldehyde
(a) Sample collected during painting
(b) Duplicate
(c) Sample collected during and after painting
(d) Sample collected 24 hr later
(e) Blank
(f) Standard, 0.25 ng
Figure 3. Chromatograms from latex-painted room - Column 2
24
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Vinyl Fabrics
The air samples collected in the vicinity of the vinyl swimming pool
lines did not contain detectable levies of vinyl chloride. Vinyl shower
curtains and vinyl pull shades were two other fabrics which were checked
as sources of vinyl chloride. The air samples removed from the closed
chambers did not show the presence of vinyl chloride although acetalde-
hyde was indicated. Temperature had no effect. Due to the negative find-
ings, no rooms containing these products were sampled.
Nursery Equipment
No vinyl chloride was detected in the analysis of air samples col-
lected from nursery environments.
Vinyl Repair and Welding
Sheets and films of polyvinyl chloride can be repaired or welded
together by the application of heat. Welding is done typically with a
stream of air heated to 260 to 290°C.
At these temperatures, it is reasonable to expect that any entrapped
vinyl chloride would be released. A study has been made by the Environ-
mental Health Laboratory,—' McClellan Air Force Base, California, which
reported that no vinyl chloride was detected at the 0.1 ppm level during
welding and meat-wrapping operations.
25
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REFERENCES
1. "Preliminary Assessment of the Environmental Problems Associated with
Vinyl Chloride and Polyvinyl Chloride," EPA-560/4-75-001, September
1974.
2. Smith, B. S., et al., "Evaluation of Vinyl Chloride Associated with
Heat Sealing PVC Products," Environmental Health Laboratory, McClellan
Air Force Base, California, Prof. Report No. 74M-17, December 1974.
26
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA 560/6-76-002
3. RECIPIENT'S ACCESSION-NO.
4. TITLE ANDSUBTITLE
Sampling and Analysis of Selected Toxic Substances;
Task III - Vinyl Chloride, Secondary Sources
5. REPORT DATE
April 1976
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
John E. Going
8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Midwest Research Institute
425 Volker Boulevard
Kansas City, Missouri 64110
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
Contract No. 68-01-2646
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Protection Agency
Office of Toxic Substances
Washington, D.C. 20460
13. TYPE OF REPORT AND PERIOD COVERED
Final. Nov. 1 to Dec. 31. 1975
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
A sampling and analysis program was conducted to determine whether and to what
extent vinyl chloride was present in ambient air due to the presence of polyvinyl chlo
ride products. Sampling environments were chosen to represent real life, but nonwork
situations where a significant exposure to polyvinyl chloride products might occur.
A sampling and analysis protocol was developed with a recovery efficiency of greater
than 90% and a detection limit of 10 ppb (v/v).
The two general categories of environments sampled were vehicles and commercial
products. The interior ambient air was sampled from new and used domestic automobiles,
foreign automobiles and domestic mobile homes. No evidence of vinyl chloride was
found. The following commercial vinyl products, when sampled in their normal environ-
ment, did not produce a measurable quantity of vinyl chloride in the ambient air:
vinyl wall covering; vinyl swimming pool liners; and vinyl nursery products. A room
being painted with a heavily pigmented red paint was found to contain a very low
level of vinyl chloride.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Monitoring - Air
Vinyl Chloride
Organic Chemistry
18. DISTRIBUTION STATEMENT
Release Unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
30
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
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