ENVIRONMENTAL
EVALUATION
OF
VINYL CHLORIDE EMISSIONS
IN THE
LONG BEACH AREA CALIFORNIA
FEDERAL FIELD INVESTIGATIONS CENTER-DENVER
DENVER . COLORADO
AND
REGION IX - SAN FRANCISCO CALIFORNIA
MAY 1974
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PREFACE TO REGIONAL MONITORING REPORTS
ON VINYL CHLORIDE
This is a preliminary report and should not be construed
to represent Agency policy. When reading this document it
should be recognized that this information was obtained in a
very short period of time using sampling and analysis methods
that have received only a limited amount of pretesting. The
methods utilized were based on the Agency's best scientific
judgement and represent, in the Agency's opinion, the best
methods available. However, they have not been thoroughly
tested for accuracy and precision under field conditions. The
actual sampling and analysis methods were based on previous
analytical studies in which similar chemicals were evaluated.
Prior to and during the actual vinyl chloride sampling and
measurement only limited quality control and standardization of
procedures could be applied in the time available. It is impor-
tant to recognize that the methods utilized are interim proce-
dures which are subject to further modification. In addition,
the methods should not be construed as EPA recommended methods.
The nature of the PVC manufacturing process results in the
escape of vinyl chloride in pulses; therefore, high levels may
appear in grab samples taken at the time of these releases, and
very low levels may be present at intervening times. So, too,
changes in air movement may influence concentrations at a given
station at any one time. Therefore, it is important to recognize
that the vinyl chloride data reported in this document are prelimi-
nary in nature and are subject to change as additional monitoring
is performed under more representative and standardized conditions,
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ENVIRONMENTAL PROTECTION AGENCY
EVALUATION OF VINYL CHLORIDE EMISSIONS
IN THE
LONG BEACH AREA, CALIFORNIA
NATIONAL FIELD INVESTIGATIONS CENTER - DENVER
DENVER, COLORADO
AND
REGION IX - SAN FRANCISCO, CALIFORNIA
MAY 1974
-------
CONTENTS
Page
I. SUMMARY 1
II. INTRODUCTION 3
III. PLANT EVALUATION 7
American Chemical Corporation 7
B.F. Goodrich Chemical Company 11
IV. SAMPLING PROGRAM 15
Wastewater IS
Air 17
V. RESULTS AND DISCUSSION 20
APPENDICES:
A - TEST PROCEDURES
B - PLANT EVALUATION - KEYSOR-CENTURY CORPORATION
C - PERSONS CONTACTED
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EVALUATION OF VINYL CHLORIDE EMISSIONS
IN THE LONG BEACH AREA, CALIFORNIA
I. SUMMARY
A survey of vinyl chloride emissions from the American Chemical
Corporation and B.F. Goodrich Chemical Company showed that vinyl
chloride monomer was leaving the plants via water, sludge, and air as
well as in the final produce, polyvinyl chloride.
It is estimated that about 2.3 kg (5 lb)/day of PVC leave the
B.F. Goodrich plant, and 10 kg (22 lb)/day leave the American Chemical
plant in the wastewater effluents. Smaller quantitied were found in
the sludge.
Vinyl chloride monomer was released to the air during venting,
cleaning, or by accident. One on-site release monitored by infrared
spectrometer reached approximately 75 ppm at the point of measurement
in-plant. The mean value of all grab samples collected was about 0.1
ppm; the maximum value measured was 3.4 ppm, 4.8 km (3 mi) north of the
plants. To maintain the 0.1 ppm level over the area of the study
(4.8 km radius) would require about 910 kg (2,000 Ib) of VCM. Each
exchange in the basin must be renewed by this quantity to maintain
the 0.1 ppm level. Thus, if the exchange of air in the area occurred
four times a day, a minimum of 4 tons of VCM would have been discharged
from these plants.
The survey also indicated that the plants will routinely be in
violation of the standard proposed by the Occupational Safety and
Health Administration which requires the level of employee exposure to
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vinyl chloride to be undctectable. About 5 percent of the ambient air
samples exceeded 1 ppm VCM and in-plant releases from 20 to 75 ppm were
measured.
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II. INTRODUCTION
Vinyl chloride is used primarily in the production of polyvinyl
chloride for floor tile, records, pipe, containers and other plastic
products. It is also used as aerosol propellent in consumer products
such as pesticide and hairspray.
Potential environmental and health hazards are associated with
the vinyl chloride industry- Vinyl chloride has been implicated in
both worker and nonworker deaths from a rare but fatal form of cancer,
angiosarcoma of the liver. A recent study in animals has tentatively
indicated that exposures to this chemical in concentrations as low as
50 mg/1 tends to produce carcinogens. These data have led the Occupa-
tional Safety and Health Administration (OSHA) to propose a standard
for employee exposure to vinyl chloride at no detectable level
(39 FR 16896, 10 May 1974).
The Administrator of the Environmental Protection Agency (EPA),
Russell Train, established a task force under the chairmanship of the
Director, Office of Toxic Substances, to determine what action EPA
should take to preclude or reduce the hazards caused by vinyl chloride.
A major task force objective was to collect monitoring data for the
kinds and levels of air emissions, wastewater effluents, and sludges
from vinyl chloride and polyvinyl chloride plants and ambient data on
the pollutants from these plants.
On 10 April 1974 the Director, Office of Toxic Substances, asked
the Region IX Administrator to assist in assessing the extent to which
vinyl chloride in process wastes is being introduced into the environment.
-------
The requirement for analytical results by 20 May prompted a 24 April
request by Region IX for assistance from the National Field Investi-
gations Center - Denver in conducting the analysis of effluent and
sludge samples and ambient air monitoring in the vicinity of two
plants, the American Chemical Company and B.F. Goodrich Chemical
Company plants in Long Beach, California.*
The B.F. Goodrich and American Chemical plants are next to each
other in a highly industrialized area of Long Beach. General land use
in the area is shown in Figure 1, and the plot plan of the plant prop-
erty is in Figure 2. Both plants operate around-the-clock, 7 days a
week. Residential areas lie within half a mile of the plant.
The "1974 Directory of Chemical Products, USA" indicates that the
B.F. Goodrich plant has an annual capacity of 73-million kg (160-million
Ib) of polyvinyl chloride resins. The American Chemical plant has an
annual capacity of 68-million kg (150-million Ib) of polyvinyl chloride
in addition to a 79-million kg (175-million Ib) capacity for vinyl
chloride monomer.
On 6 May, Region IX and NFIC-D staff members met representatives
of each of the plants (App. C) to discuss industrial processes, and
to determine possible points for sampling to be conducted 7-10 May.
* There are three vinyl chloride plants in Region IX. The Keysor-Cen-
tury Corporation at Saugus, Cal. was visited on 30 May 1974, but it
was not sampled; the plant evaluation is in Appendix B, and Plant
personnel contacted are given in Appendix C.
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,
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d.
01
-fl-
AMERICAN CHEMICAL
CORPORATION
B.F.GOODRIGH
CHEMICAL COMPANY
Figure 2 • Properly Layout
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III. PLANT EVALUATION
AMERICAN CHEMICAL CORPORATION
Manufacturing Process and Sources of Waste
The American Chemical Corporation plant manufactures four products:
ethyl chloride, ethylene dichloride (EDC) by two methods, vinyl chloride
monomer, and polyvinyl chloride by suspension polymerization [Fig. 3].
In the manufacture of ethyl chloride, the raw materials are ethy-
lene, hydrochloric acid and aluminum chloride as the catalyst. Only
non-contact cooling water is used in the process. Unreacted hydro-
carbons and hydrochloric acid are vented through a scrubber. Off-gases
from the scrubber go to the incinerator.
In the manufacture of EDC by direct chlorination, the raw materials
are crude ethylene and chlorine. In this process, the water from the
oxychlorination process is used to wash the feed to the reactor. This
wastewater is then neutralized and sent to the sewer system. The vent
gases from this unit go to the oxychlorination system and through an
incinerator. The carbon steel vessels act as a catalyst in this process.
The manufacture of EDC by the oxychlorination process uses ethylene,
hydrochloric acid and air as raw materials, and cupric chloride as a
catalyst. As in direct chlorination, the acid water from the oxychlor-
ination reactor is used to wash the ethylene dichloride in an inter-
mediate purification step. All of this water is neutralized and sent
to the sewer system. The combined water from both units currently
contains about 200 mg/1 EDC. By July, steam stripping will be installed
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'«.•... C.-s
Fr^_
Sef: -er
Etf-ylene
(CcW Bex)
Ethyl Chloride Unit
Direct Chlorination
Chlorine
Reactor
Ethylene Oichloride Units
Oxychlorination
Wastewster to
Sanitary
L Acidic Uater !
— — —— — — — —— __ —_ __ ^ -_ _ __ _J
EDC For Vinyl Feedstock
Wastewater to
Sanitary Seuer £ Ground Drains
to
Sanitary Sewer
Wasteviater to
Sanitary Sewer
vinyl Chloride for »/C Feed Stock
Figure 3 -flnencan Cieraical Corporation Process Flow
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to lower the EDC to 25 mg/1. All vent gases from this unit go through
the incinerator.
There arc three vinyl chloride monomer units on the plant site,
but only one was operating during the visit. Production capacity of
this unit is approximately 45-miilion kg (100-million Ib) of vinyl
chloride per year. The VCM production rate during sampling was esti-
mated at 90 percent of this capacity. The VCM units use EDC as the
raw material. For drying, the vinyl chloride monomer passes through a
caustic system which is blown down once per shift and discharges 38 to
57 liters (10 to 15 gal.) of caustic to waste for neutralization.
The plant has three PVC suspension units, three centrifuges, and
three dryers. The two horaopolymer units use VCM as the raw material,
tertiary butyl peroxide as catalyst-, and methyl cellulose and carboxy-
methyl cellulose as disperring agents (CMC is used once-through). The
copolymer unit uses VCM and vinyl acetates a mineral spirits catalyst,
and trichloroethylene as a modifier. The three PVC dryers produce dry
polymer at a total rate of about 6,800 kg (15,000 lb)/hr. The dryers are
the limiting factor in PVC production.
After polymerization, the PVC slurry is discharged into a blowdown
tank where the unreacted momoner is stripped by vacuum and recycled to
thePVC reaction vessel. An incinerator and scrubber prevent escape of
vented VCM to the atmosphere. The PVC is separated from the water by
centrifuging, dried in rotary steam-heated dryers, and stored for sales.
The vent gas from the rotary dryer goes to the bag house for
separation. The air from the bag house and storage area goes through a
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10
particulate filter at a flow rate about 57 m3/min (2,000 cfra). All
PVC units have VCM recovery units. When the PVC reactors are to be
opened, the vinyl chloride left in the reactor is discharged through
steam jets to the atmosphere.
Sources of process wastewater are the caustic blowdown from the
vinyl chloride process, acid washwater used to remove ferric chloride
from the EDO before its distillation, effluent from the PVC slurry
centrifuging units, surface drainage (washwater) from the VCM recovery
units, the PVC plants and the chlorination units, and effluent from
the VCM incinerator flue gas scrubber.
The plant uses water at a rate of 38 to 41 I/sec (600 to 650 gpm).
The total wastewater flow* is about 19 I/sec (300 gpm), of which 6 to
8 I/sec (100 to 130 gpm) results from the centrifuge units cited
above. The remaining water is lost through cooling tower evaporation.
Treatment System
The plant is equipped with separate industrial, storm, and sani-
tary sewer systems. Three separate basins are used to neutralize
wastewater from the different processes. One of these, the Dominguez
Channel pumping basin, receives rain and outdoor plant runoff water
in addition to surface drainage from the PVC and chlorination units.
Overflow into Dominguez Channel does not usually occur except during
heavy rains or periods of excessive plant washdown. The effluent from
the three basins is collected in the West Sanitary Sewer interceptor
* The only flow measurement available in the facility was the total
flow at the pll check basin.
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11
basin, and the pH is again adjusted before the effluent is discharged
to the Los Angeles County Sanitation District for primary treatment.
The wastewater effluent has a COD of 600-800 mg/1 and a TSS of about
1,000 mg/1. The majority of these suspended solids are from the sus-
pension polymerization of PVC.
All off-gases from ACC go through the single stage incinerator
which operates in the 760to870°C (1,400 to 1,600°F) range and has an
after scrubber to remove hydrochloric acid.
Solid waste from plant operations is trucked by contract disposal
to approved landfills. The sludge and liquid removal rate is about
32 m3 (8,400 gal.)/week of combined sludge and water; the water con-
tent ranges from 50 to 80 percent.
B.F. GOODRICH CHEMICAL COMPANY
Manufacturing Process and Sources of Waste
The B.F. Goodrich Chemical Company plant, on a 12-acre site,
manufactures polyvinyl chloride resins and compounds. PVC is made
using batch suspension polymerization; VCM (purchased) reacts with
water, emulsifiers and initiators, under controlled conditions of
temperature and pressure [Fig. 4]. The raw materials used in the
reaction are an organic peroxide catalyst, a polyvinyl alcohol dis-
persing agent, and phthalate plasticizers.
After the reaction is complete, the unreacted vinyl chloride is
stripped, condensed, and recovered for recycle. The stripped resin
is then transferred to tanks for blending of the resins from numerous
reaction vessels. To this point the process is batch. The remaining
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Raw
Materials
VCM
H20
Catalyst
Reactor
Washwater
To Sev;er
VCM
Recovery
Reactor
24
Each
To ATM
Refrig.
Vent
Condenser
Recycle
VCM
Reactor
•*»- ATM
Vent
Sanitary Sewer
To ATM
To ATM
To ATM
Blend
Tank
Wash water
To
Sewer
1
Blend
Tank
7 Each
i
Centrifuge
i
Wastewa
Dryer
4 Each
ter to
Compounding
Extruders
j
Dust
Control
k
Polymer
To
Storage
Figure 4 - B.F.Goodrich P.V.C. Process Flow
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13
process steps are continuous. The resin is pumped from the blend
tanks to a centrifuge for dewatering. The wet cake from the centrifuge
then enters a hot air dryer equipped with appropriate dust control
devices. The resin is then either bagged for shipment, or transferred
to storage silos for bulk shipment or subsequent compounding.
3
Each of the 24 reactors at the plant is a 9.5 m (2,500 gal.)
vessel. Vapors from these reactors pass through the VCM recovery
system and refrigerated vent condensers. Reactors are evacuated before
being opened for washing; upon opening, they are vented to the atmo-
sphere. This cycle occurs 2 or 3 times a day per reactor, a total of
about 50 times. This plant produces 7-million kg (15-million lb)/mo
of homopolytner PVC, part of which is plasticized with a phthalate
plasticizer.
All water used at B.F. Goodrich is supplied by the city. Total
plant water effluent rate was determined by subtracting an estimated
15 percent evaporation from the city water inlet rate, obtained by
reading the city water meter. During sampling, this effluent rate
o
was approximately 490 m /day (.13 mgd). The plant uses cooling towers
and generates steam for process uses. Each reactor uses 2,300 to 3,000
liters (600 to 800 gal.) of water per wash. The cooling tower blow-
down, containing a chromium inhibitor, and the boiler blowdown, contain-
ing phosphate-sulfite, are discharged to the sewer system. All cooling
water, except the water used in the compounding area, is non-contact.
The contact water used in the compounding area is recycled to the
cooling tower except for the 130 1/min (35 gpm) discharged to the
sewer.
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14
Major wastewater sources are: centrate from dewatering centri-
fuges (PVC), reactor cleaning, general cleanup of equipment and floors,
discharge from the wet scrubber dust control system, water treatment
system regenerate, and boiler blowdown.
The water discharged from the centrifuges is the major source of
waste effluent, with a flow of 260 to 300 1/min (70 to 80 gpm). About
130 1/min (35 gpm) wastewater comes from the wet scrubber in the com-
pounding area. The effluent has a COD of 80 to 150 mg/1, and 500 to
600 mg/1 suspended solids. The suspended solids are mainly fine parti-
cles of PVC from the suspension polymerization.
Treatment System
The plant is equipped with separate industrial, storm and sanitary
sewer systems. After neutralization and gross removal of suspended
solids, the industrial wastewater discharges to the Los Angeles County
Sanitation District for primary treatment. Except for excessive rain-
fall, the storm sewer discharge is recycled as cooling tower makeup.
Atmospheric emission points from the PVC process are vents from
reactor vessels, the monomer recovery system, blend tanks, compounding
dust control and ventilation systems, and dryer dust collection systems.
Solid waste from plant operations is trucked by contract disposal
to approved landfills. About 3,600 kg (8,000 Ib) of the resin and water
sludge are removed every 6 weeks. Water content of the sludge is about
50 percent.
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15
IV. SAMPLING PROGRAM
WASTEWATER
Three sampling stations were established at the B.F. Goodrich
plant and seven at the American Chemical plant. Sampling of effluents,
city water and sludge were conducted by Region IX, Surveillance and
Analysis Division personnel for a three-day period, from 10:00 a.m.
on 7 May 1974 until 9:00 a.m. on 10 May 1974. Sample point selections,
frequency of sampling and methodology were based on guidelines pro-
vided by the EPA task force. In general, effluents leaving the plant
property and discharging into the county sanitary sewer system or
into surface waters were to be sampled hourly around-the-clock for
three consecutive days. During the three-day sampling period no dis-
charges to surface waters occurred, and it was necessary only to take
around-the-clock samples of streams to the sanitary sewers.
Hourly samples for eight consecutive hours during each of the
three sampling days were taken from 10:00 a.m. to 6:00 p.m. at in-plant
pretreatment points, such as settling basins. Grab samples of influent
city water and sludge from settling basins were taken once each day.
Eight-hour composite samples (taken hourly) were obtained on the after-
noon shifts of 9 and 10 May 1974 (6:00 p.m. to 2:00 a.m.) for metals
analysis and preserved with nitric acid in cubitainers.
All samples for VCM analysis were taken manually by filling each
sample container to the brim directly from the stream.
Water samples were collected in 50-ml, acetone-rinsed, glass
bottles with teflon-lined caps. Sludge samples vrere collected in
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16
acetone-rinsed jars with teflon liners. The samples were refrigerated
(approx. 0 to 3°C) after collection and protected from light. Because
vinyl chloride is a gas at ambient temperatures, samples were not
composited* but rather were analyzed individually. Chain-of-custody
procedures were followed throughout. The following table gives sample
number, description, and sampling frequency.
Sample Description Daily Frequency
B.F. Goodrich Chemical Company
G-l Plant effluent at interceptor 24 consecutive hourly
pit grab samples
G-2 City water 1 grab sample
G-3 Interceptor pit sludge 1 grab sample
American Chemical Corporation
AC-1 Plant effluent at pH check 24 consecutive hourly
basin grab samples
AC-2 Ground drains from PVC and C12 8 consecutive hourly
units grab samples
AC-3 Neutralized VCM and EDC waste- 8 consecutive hourly
water grab samples
AC-4 PVC centrifuge effluent 24 consecutive hourly
grab samples
AC-5 Pumping basin overflow Not used
AC-6 City water 1 grab sample
AC-7 Sludge from PVC centrifuge 1 grab sample
The two sets of 8-hr composite samples for copper and mercury
analysis were collected at stations G-l, and AC-1 through AC-4. Both
metals are commonly used as catalysts in the production of vinyl
chloride. Analytical test procedures are discussed in Appendix A.
* Results shown as composites in the table above will in fact have been
averaged over the sample period.
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17
AIR
Air sampling was conducted by personnel from NFIC-D. Ambient air
quality was evaluated by 10-min grab sampling, 24-hr composite sampling,
and continuous air monitoring was conducted on the plant properties.
Figure 5 shows the location of the ambient air sampling stations. Chain-
of-custody procedures were used for all ambient air samples.
The grab samples were collected at 15 locations surrounding the
plant to a distance of 5 km (3 mi) downwind. Each day (four sampling per-
iods) the sampling schedule was altered by shifting the sampling run 2 hr.
Thus over the 3-day period, the 12 samples collected at these locations
showed collection times approximately 2 hr apart. Samples were collec-
ted by drawing air through MSA Organic Vapor Sampling Tubes (small
carbon columns of activated coconut char) for 10 min using a precali-
brated portable pump. From 2.3 to 4.0 1 (.08 to .14 ft ) of air was
passed through each tube for later analysis. After sampling, the tube
was capped, tagged, placed in a polyethylene bag, and cooled on dry ice
until analyzed at NFIC-D.
For the 3-day period the 24-hr composite samples were collected
at six locations [Fig. 5] on large carbon columns prepared at NFIC-D.
Each column consisted of three sections containing approximately 1.5 gm
each of Nuchar WV-L, 8/30 mesh granular activated carbon separated by
glass wool. The carbon was activated at 600°C for 1/2 hr before being
charged in 7 mm glass tubing previously rinsed in acetone. After being
charged, the tubes were heat-sealed and ready for use. In the field
the tube was broken open, one end covered with a rubber serum cap and
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r V \|f ;.'.r;-*,=U.~V<
; -:x\ . M, v. *"•-"•" \j
_
r - p' T\ Vi-
' ^-
STATIONS 3911 • 3808 24 HOUR COMPOSITE SAMPLES ••?/.
STATIONS 3911 • 392! 10 MINUTE GRAB SAMPLES
•'/ (' I^U-ftlr' • f
> I • -V ' :: js ", i :/ . '• < ?T
f* I «. i L ;' • : . / : •'
1 ' ( •/;: i ?• "'I P
I *"ii f •/rM*-»jLt'-
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19
a 30-gage hypodermic needle connected to a vacuum pump inserted for
flow control. The hypodermic needles had been previously calibrated
at 77cc/min ± 5 percent. After each sampling period the tubes were
closed with masking tape and placed on dry ice until returned to NFIC-D
for analysis. Hypodermic needles were also returned for recalibration.
During the second and third sampling periods the tubes were covered to
prevent exposure to sunlight.
Continuous analysis was possible using the Wilks Scientific MIRAN
Portable Gas Analyzer*. The instrument is a single-beam, infrared
spectrometer with folded path gas cell and a wavelength range of 2.5
to 14.5 urn. Vinyl chloride can be detected at 6.15, 9.8, 10.9, and
13.9 ym with varying sensitivites and interferences; the minimum
detectable concentration is about 1 ppm. Coupled to a strip chart
recorder, the instrument is capable of continuously monitoring a var-
iety of atmospheric pollutants. In this case the instrument and recorder
were set to measure vinyl chloride at ACC on two occasions for 14 hr
and 21 hr, and at BFG for one period of 21 hr. The instrument was also
operated for a short period of 2 hr in a sedan parked about 0.5 km
(0.3 mi) due east of the plant.
* Citation of brand name or trademark does not imply product
endorsement.
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20
V. RESULTS AND DISCUSSION
WATER SAMPLES
The results of the analyses and compositing of water samples from
both plants are given in Table 1. The maximum values shown are the
highest individual values used in determining the composite since each
hourly aliquot was analyzed separately. The average concentrations of
VCM in the effluent from both plants (Stations G-l and AC-1) are quite
comparable, although the extremes at B.F. Goodrich are more than twice
as high. Since the variability in flow rate as measured hourly at
station AC-1 was not large Cabout ± 10 percent), little error is intro-
duced by not flow weighting individual results. Daily average flow
rates at ACC were calculated as 21, 20 and 21 I/sec (330, 310, 330 gpm)
for the 3 days of the survey.
Since sampling locations were open to the atmosphere, a certain
amount of vinyl chloride would be expected to be transferred to the air
at these sites or at other locations where turbulence was experienced.
Also, since there is no partial pressure of VCM above the water surface,
the gas would be expected to transfer from water to the air in the sewer
system. From there it would vent to the atmosphere through manhole
covers or even at the sewage treatment plant. At a flow rate of
20 I/sec (320 gpm) from ACC and 6 I/sec (90 gpm) from BFG, the amount
of VCM leaving the plants via the water route is estimated to be
10 kg (22 lb)/day from ACC and 2.3 kg (5 lb)/day from BFG.
Two 8-hr composites for copper and mercury analyses were collected
at Stations G-l, and AC-1 through AC-4. No mercury was found at either
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21
plant, but copper, presumably resulting from the cuprlc chloride
catalyst, was found as shown below:
Copper (mg/1)
Station AVR. Max.
AC-1 0.01 0.15
AC-2 0.01 0.05
AC-3 0.43 3.2
Table 1
Concentrations of Vinyl Chloride in Water Samples
Station
G-l
G-2
Date
(May)
7-8
8-9
9-10
7
8
9
Vinyl Chloride (mg/1]
Description
B.F.
Plant
Avg
.
Max
•
Goodrich Chemical Company
effluent -
City water
American
AC-1
AC-2
AC-3
AC-4
AC- 6
7-8
8-9
9-10
7
8
9
7
8
9
7-8
8
9
7
8
9
Plant
Ground
- grab
24 hr composite
sample
3.
5.
5.
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22
SLUDGE SAMPLES
Three grab samples of sludge were collected from the BFG inter-
ceptor pit (Station G-3) and three from the PVC centrifuge at ACC
(Station AC-7). The results from Station AC-7 showed little varia-
tion containing 4,200, 4,100 and 3,600 ug of VCM per gram of dry
sludge. The results from Station G-3 were highly variable at 290,
2,100,and 980 yg of VCM per gram of dry sludge. The higher varia-
bility and lower values at Station G-3 may be attributable to the
residence time that the particular sludge samples were in the pit.
As indicated earlier, about 3,600 kg (8,000 Ib) of sludge is removed
from BFG every 6 weeks compared to the 32 m /week (8,400 gal./week)
removed from ACC.
AIR SAMPLING
Grab Samples
Surface winds as measured hourly at the Long Beach Municipal
airport were generally from the south and the west during the survey
period. Table 2 presents the surface wind direction and speed measured
during each of the twelve grab sampling runs which took about 4 hr each.
The meteorological measurements were taken 5 min before each hour so
the Table includes the reading preceeding each run and the one immedi-
ately following completion of sampling. Wind velocity and direction
were also being continuously measured and recorded from a tower (about
100 ft high) at the ACC complex. Rough estimates of the wind velocity
and direction from these data are also shown Jn Table 2 for comparable
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Table 2
Meteorological Data
Date
Run (May)
70 7
71
72 8
73
74
75
76 9
77
78
79
80
81 10
Time
Start
1410
1930
0205
0812
1205
1822
0001
0540
1015
1535
2130
0342
(hr)
Finish
1842
2330
0610
1150
1655
2130
0335
0915
1335
1908
0120
0720
Location
IBM
ACC
IBM
ACC
IBM
ACC
IBM
ACC
IBM
ACC
IBM
ACC
IBM
ACC
IBM
ACC
IBM
ACC
IBM
ACC
IBM
ACC
LBM
ACC
v ,
-/ 1st
19
30
26
30
22
33 .
18
33
12
33
17
18
17
23
00
14
15
15
21
31
29
31
30
33
04
09
06
09
03
01
03
01
05
01
07
10
04
04
00
01
04
05
08
09
08
09
04
07
Wind
2nd
20
30
30
30
00
33
00
33
18
18
20
18
13
23
00
14
19
24
19
31
30
33
32
33
04
09
07
09
00
01
00
01
08
04
10
10
04
04
00
01
05
05
08
09
05
07
06
07
Direction / Speed (kn).
Survey Hour
3rd
24
30
30
30
20
33
20
33
18
18
18
18
15
23
00
14
20
24
24
31
30
33
29
00
07
09
03
09
04
01
06
01
07
04
05
10
04
04
00
01
07
05
06
09
04
07
04
02
4th
28
30
00
30
00
33
15
33
18
18
18
18
22
23
17
14
17
36
29
31
31
33
00
00
07
09
00
09
00
01
04
01
09
04
06
10
05
04
04
01
06
04
07
09
05
07
00
02
5th
26
30
00
30
00
33
12
33
16
18
23
18
00
23
20
15
20
36
29
31
29
33
00
09
06
09
00
09
00
01
05
01
09
04
04
10
00
04
03
05
09
04
09
09
03
07
00
01
6th
26
30
00
30
18
33
_
-
17
18
_
-
—
-
15
15
_
-
30
31
29
33
00
09
06
09
00
09
05
01
— —
—
08
04
»
_ —
—
04
05
_..
—
07
09
04
07
00
01
ro
LBM - Long Beach Municipal Airport; ACC - American Chemical Corporation
-------
24
time intervals. These two sites were about 5 mi apart on an east-
west line. There was little agreement in either wind velocity or
direction, probably as a result of differences in both elevation and
local topographic features.
Since both plants operated a series of batch processes, discharge
to the atmosphere of a continuous level of vinyl chloride would not
be expected. During any 4-hr sampling run it was only fortuitous if
the plant discharge, wind speed and direction, sampling location, and
10-min sampling period overlapped to produce a value higher than
ambient. Table 3 gives the results of each of the 10-min samples
collected during the survey period. The average and maximum value at
each station is plotted on Figure 6. Arithmetic averages were used
because of the limited amounts of information. However, data of this
sort would generally be expected to be log-normally distributed; when
all of the results were combined, this, in fact, was the case. Figure 7
shows the distribution of the results. About 5 percent of the results
exceeded 1 ppm, and about 11 percent of the data exceeded 0.5 ppm, and
the mean value is about 0.1 ppm. To attain this mean value over the
study area of 4.8 km (3 mi) radius to a depth of 50 m (164 ft) would
require 910 kg (2,000 Ib) of VCM. To maintain this level during each
exchange of air in the basin would require at least another ton of VCM.
This could easily occur several times a day. These data compare very
unfavorably with the OSHA proposal to keep limits for employee exposure
to below 1 ppm or undetectable.
Even 3 mi from the plant, individual values can reach several
parts per million. In fact, the highest value measured was 3.4 ppm
-------
Table 3
Results from ID-minute Grab Samples
[Measured in ppm at 25°C and 760 mm Hg]
Station
Distance (mi)
Run
70
71
72
73
74
75
76
77
78
79
80
81
Average
Maximum
11
1.5
0.05
0.53
0.08
0.10
0.23
0.05
0.08
0.10
0.04
0.07
0.08
0.08
0.12
0.53
12
1.1
0.15
0.06
0.29
0.11
0.15
0.48
0.04
0.19
0.24
0.10
0.11
0.24
0.18
0.48
13
1.5
0.24
0.04
0.05
0.03
0.16
0.08
0.02
0.29
0.03
0.85
0.05
0.06
0.16
0.85
14
2.8
0.23
0.06
0.04
0.04
0.04
0.05
0.02
0.11
0.32
0.18
0.08
0.25
0.12
0.32
15
2.7
0.25
0.31
0.08
0.06
0.12
0.10
0.20
0.55
0.08
0.26
0.07
1.2
0.28
1.2
16
3.1
0.25
0.14
0.08
0.13
0.45
0.16
0.05
0.04
1.4
0.17
0.03
0.02
0.25
1.4
17
3.1
0.06
<0.01
0.33
0.29
0.21
3.4
0.06
0.53
0.69
0.08
0.02
0.10
0.53
3.4
18
1.1
0.05
0.21
0.08
2.7
0.05
0.23
0.03
0.98
0.31
0.12
0.03
0.04
0.41
2.7
19
1.9
0.05
0.40
0.10
0.03
0.04
0.16
0.06
0.16
0.33
0.05
0.05
1.7
0.26
1.7
20
0.7
0.11
0.02
0.08
0.37
2.1
0.05
0.06
0.36
1.1
0.02
0.02
0.06
0.36
2.1
21
0.9
0.11
0.05
0.04
0.26
0.08
0.07
0.22
0.45
0.08
0.24
0.03
0.04
0.14
0.45
22
0.5
0.21
0.02
0.02
0.16
0.03
0.03
1.1
0.07
1.0
0.08
0.07
0.84
0.30
1.1
23
0.6
0.05
0.05
0.08
0.34
0.11
0.25
0.15
0.04
0.50
0.03
0.05
0.15
0.15
0.50
24
0.6
0.11
0.06
1.0
0.08
1.3
0.06
0.07
0.05
0.14
0.02
0.03
1.1
0.33
1.3
25
1.3
0.03
0.04
0.10
0.01
0.09
0.09
0.48
0.15
0.03
0.06
0.07
0.33
0.12
0.48
to
Ul
-------
(Vista del Mar %w • <° ir":Vvr
•2!:: M
•»*• . . >_ ••• .1 3-
• •• «JY.!.:". -^:;;f:' '< ;.
'
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»«""»: \'--°." '*•
,., Memwul P«* \j $ -, - j
-- •- i,±*>'H, ,
E G E N D
STATION
0.12 AVERAGE
0.32 MAXIMUM • ppm
%1 j 0 '? : cTI ' !'| ^-4*"" \if**?J ft//! /• °-32 MAXIMUM - ppm '( -- ^j. f ' f|';'|'.1
fe-.
Figure 6. • Concentrations of Vinyl Chloride in Air Samples
-------
B
Z
0
a.
\-
z
u
u
Z
0
u
5
O
I I I
3.0
2.0
1.0
0.8
0.6
0.2
0.
.08
.06
.04
I I II I I I
I T
I I
O
I
I
I I
J I
10 30 50 70 90
PERCENT OF DATA < TO STATED VALUE
98 99
Figure 7 • Distribution of Grab Sampling Concentrations
-------
28
at a site 4.8 km (3 mi) due north of the plant (Station 17). This may
have been due to a minor accident that occurred during the survey period
at the B.F. Goodrich plant when a small pipe ruptured on a PVC reactor
vessel (to be discussed later). It should be noted that since the VCM
was collected on carbon columns, the values stated will be minimums.
Adsorption and desorption efficiencies and any other losses will com-
bine to minimize reported values.
In general, a relationship was seen between sample concentrations,
wind direction, and speed; however, since each run could not provide
synoptic data and since meteorological information was minimal, further
analysis such as isoconcentrations and dispersion was unprofitable. In
addition to VCM, the sampling tubes were also capable of collecting
trichloroethylene. This was observed at least once at all locations
except Station 23. The highest value observed was about 1.2 ppm.
While usually associated with the higher values of VCM, high values of
VCM did not always assure the presence of trichloroethylene.
Composite Samples
In general, results of the 24-hr composite sampling [Table 4] were
lower than comparable grab sampling stations nearby. As noted with
the grab sampling analyses the results will be minimum values. These
values assume a 100 percent adsorption/desorption efficiency not yet
validated by the laboratory and actually doubtful. With the exception
of Station 06 all composite samples were no less than 50 percent of the
nearby grab sample station results. Station 06 showed high values on all
3 days with an average that was five times higher than the other com-
-------
29
posites and over 60 percent higher than that of the nearest grab
sampling station. While the station was almost due west of the plant,
the meteorological data does not show conditions that should make
these results an order of magnitude higher than other downwind stations.
This sampling site was at a service station with access to the wide
variety of vapors from the shop area. The VCM may be absorbed and thus
concentrated by petroleum fumes. This could then produce a higher
concentration per unit volume of sample as both air and fumes are
collected on the carbon column. This situation may be an occupational
hazard that bears further study.
Table 4
Composite Sample Results
Station
01 .
02*'
03
04
05
06
^12-hr
Distance from Plant
(mi)
1.9
0.7
0.8
3.3
2.7
2.8
composite
May 7
.08
.08
.07
.27
VCM
May 8
.06
.07
.08
.04
.06
.65
(ppm)
May 9
.05
.10
.05
.05
.05
.27
Average
.05
.08
.07
.05
.05
.40
Continuous Sampling
The use of the infrared spectrometer proved valuable in indicating
levels that might be expected to emanate from each plant. Before this
study there had been no operating experience in the use of this instru-
ment at NFIC-D, so several modifications are still desirable to adapt
the instrument to total field use.
-------
30
As originally envisioned, the instrument would be most valuable
during grab sampling to give immediate indications when high concen-
trations, or hot spots, of vinyl chloride were present. This would
permit sampling at a given location, such as Station 17 on run 75,
during periods of particular significance. However, quantitative
results were difficult to obtain during initial trials due to engine
noise when the instrument was operating from a vehicle. Further
modifications to filter the noise will be necessary before maximum
use of this instrument can be realized.
During a 14-hr period of operation at ACC the instrument went
off-scale only once for about a 1-min period when vinyl chloride
was vented in error. The concentration in this period showed no other
significant readings from background. During a 21-hr period of opera-
tion at BFG the instrument detected several releases at about 20 ppm,
several at 25 ppm, one at 30 ppm and a 10-min release that reached
as high as 75 ppm. Other than the latter, which vented from a ruptured
pipe, these readings were probably the result of venting the reactors
to the atmosphere during cleaning operations. The meteorological data
at ACC during the time of this release (8 May, 1855 - 1905 hr) indicated
winds to the north at about 9 kn. Thus the team at Station 17 due
north of the plant at 1942 hr was probably sampling this discharge when
it collected the grab sample with the maximum value observed.
Unlike the carbon column, the infrared spectrometer measures a
maximum possible value rather than a minimum. This occurs since other
organics will register in the same region of the spectrum as VCM to
-------
31
varying degrees. Thus, at the 10.9 pm wavelength at which these
measurements were taken, vinyl acetate, trichloroethylene and ethylene
would be interferences because they would also register in an additive
manner. However, none of these are thought to be used at the B.F.
Goodrich plant where the major releases were measured. For precise
measurement with this instrument, the magnitude of these interferences
must be known 1) so that a correction can be made, or 2) to determine
that other wavelengths less sensitive to the interference must be used.
-------
APPENDIX A
TEST PROCEDURES
-------
A-l
Appendix A
TEST PROCEDURES
Water Samples
Water samples were tested for acid-extractable metals following
procedures described in the EPA manual "Methods for Chemical Analyses
of Water and Wastes," July 1971. Copper content of the water was
determined by atomic absorption spectroscopy and mercury content by
the cold vapor technique.
Vinyl chloride and trichloroethylene were measured in water by
directed aqueous injection gas chromatography using a hydrogen flame
ionization detector. Using the chromatographic conditions described
below, the minimum detectable concentrations were 0.1 mg/1 for vinyl
chloride and 10 mg/1 for trichloroethylene. The presence of vinyl
chloride in the water samples was confirmed using a Finnigan Model
1015 Gas Chromatograph/Mass Spectrometer System (see attached mass
spectra).
Standard solutions of vinyl chloride were prepared by bubbling
vinyl chloride gas (Matheson Gas Company lecture bottle) into a cold,
tared 50 ml sample of distilled water for one to two minutes. The
water was reweighed and refrigerated. Normally, these standard solu-
tions would contain approximately 4 mg/ml of vinyl chloride. Working
standards were prepared by adding the standard vinyl chloride solu-
tion to cold 1 ml water samples in septa-seal vials which were sealed
immediately and rerefrigerated until used (within 1 hr). All samples
-------
A-2
and standards within the 1 to 15 ng/ul range varied about 5 percent
from day to day. Standards prepared in organic solvents gave
responses twice that of comparable water standards. Quantitative
measurements were made using peak height comparison of standards
and samples.
Instrumental Condition
Instrument - Varian Model 1400
Column - 6' x 2 mm glass packed xfith 80/100 mesh Porapak Q
Carrier Gas - Helium at 20 ml/min
Column Temperature - 150°C
Injector Temperature - 200°C
Detector Temperature - 250°C
Under these conditions, vinyl chloride eluted in approximately
1.4 min and trichloroethylene in 15.2 min.
Air Samples
Vinyl chloride and trichloroethylene concentrations in air were
measured by adsorption of the organic vapors on activated charcoal.
The organics were eluted from the carbon with carbon disulfide which
was then analyzed by gas chromatography using a hydrogen flame ioni-
zation detector.
Standard solutions were prepared by bubbling vinyl chloride
(Matheson Gas Company) into cold, tared, toluene for approximately 15
sec. The toluene solution was reweighed and the amount of dissolved
vinyl chloride was determined by weight difference. Working standards
were prepared by diluting the cold reference solution with cold CS2
-------
A-3
in cold vials. Aliquots of the working standards were immediately
pipetted into septum capped vials where they were found to be stable
for about 8 hr. Each of the small charcoal sections was added to one
ml of cold CS,, in a vial; the vial was capped and analyzed after 1/2 hr.
The large sections were added to 25 ml of cold CS- and after standing
in the cold for 1/2 hr an aliquot was withdrawn and placed in a capped
vial for gas chromatographic analysis. Quantitative measurements were
made using a Hewlett Packard Model 3352-B computerized system after
computer calibration using the working standards described. Under
these conditions vinyl chloride eluted in 0.9 min and trichloroethy-
lene in 3.2 min. For the small columns, detection limits were 0.05 ug
for vinyl chloride and 5 yg for trichloroethylene. For the larger
columns, the detection limits were 1 ug for vinyl chloride and 130 pg
of trichloroethylene.
Instrumental Condition
Instrument - Hewlett Packard Model 5711
Column - 10' x 1/8" stainless steel packed with 6 percent OV-101
on 60/80 mesh Gas Chrom. Q
Carrier Gas - Helium at 25 ml/min
Oven Temperature - 50°C isothermal
Injector Temperature - 100°C
Detector Temperature - 150°C
Solid Samples
Solid samples were dewatered by filtration through a Buchner
funnel. A portion of the wet cake was set aside for moisture deter-
mination while a separate portion (10 g) was extracted with
-------
A-4
tetrahydrofuran (100 ml) in an explosion-proof Waring Blender. A
1-ml aliquot of the cold THF extract was added to a cold septa-seal
vial which was capped and analyzed by gas chromatography using a
hydrogen flame ionization detector. Instrumental conditions and
standards were the same as described for the air sample analyses.
The identification of trichloroethylene was not possible using this
procedure since the retention time is similar to THF, and consequently,
the solvent completely masked any trichloroethylene that may have been
present.
-------
S'ECTHJH f^JTSER 35 - 32
G-l 2126
8
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o
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S0 €9 70 83 S3 103 110
MX E
Figure A-1 , EJass Spectra^ of Vinyl C&ioride Standard
-------
NUS^ER -50 - 3S
VINVL CHLORIDE S7D
O
-------
APPENDIX B
KEYSOR-CENTURY CORPORATION
PLANT EVALUATION
-------
B-l
Appendix B
KEYSOR-CENTURY PLANT EVALUATION
The Keysor-Century Corporation operates a polyvinyl chloride and
record manufacturing plant about 40 mi north of Los Angeles at Saugus,
Cal. The plant produces about 40 million Ib/yr of PVC. About 90 per-
cent of the product is used at the plant for the manufacture of records.
The remaining 10 percent is sold for the production of floor tile.
The PVC plant employs 15 people, and the other 200 plant employees work
in the record manufacturing facilities making specialty records for
various government agencies, the military, and other groups.
Manufacturing Process and Sources of Waste
The PVC plant operates around-the-clock 7 days/week. The PVC
copolymer is produced from vinyl chloride and vinyl acetate by suspen-
sion polymerization in twelve batch reactors [six 7,500 1 (2,000 gal.)
and six 15,000 1 (4,000 gal.)]. Additives include a gelatin suspension
agent, the deconal peroxide catalyst and trichloroethylene as the chain
transfer agent. Reaction time for the small batches averages 4 hr and
the large batches averages about 6 to 8 hr. The excess VCM and vinyl
acetate in the reactors are recovered under pressure and vacuum respec-
tively; condensed in chilled water cold traps, and recycled. The reactor
batches are directed to open slurry tanks where the resin is held in
suspension until centrifuged. The reactors are cleaned with ethylene-
dichloride which is then recovered and processed for reuse.
There are two parallel drying systems to accommodate the resin-
water slurry produced, each complete with a centrifuge, flash dryer,
-------
B-2
cyclone, screening equipment and baghouses for particulate emission
control. Dried resin for in-plant use is transferred to holding silos
for temporary storage. From the holding silos it is conveyed to the
weighing hopper where it is weighed for compounding and use in record
manufacture. Resin for sales is held in storage silos to await ship-
ment. Figure B-l is a process flow diagram.
Process wastewater originates from the two PVC resin centrifuges
and boiler blowdown and is discharged at approximately 170 1/min (45
gpm) into the sanitary sewer system. Surface drainage sources of non-
contact wastewater averages 220 1/min (60 gpm). This results from
plant washdown, external spraying of the reactors for supplemental
cooling, cooling water blowdown and pump seal cooling water.
Treatment System
Process wastewater is discharged directly to the Los Angeles
County sanitary sewer system, Area 26 in Saugus.
Surface drain water currently flows into the Santa Clarita River,
but the company plans to combine this with the process waste-water and
discharge both streams into the sanitary sewer system in order to sim-
plify the system and to eliminate intermittent "septic-type" odors
which are suspected to originate from stagnent areas in the surface
drain system. The odors have not been positively identified, but the
company states they are definitely not vinyl chloride monomer. No
odors were detectable during the plant visit.
If the odors persist after the streams are combined and the source
of odors is positively identified, odor removal capability will be
-------
RECYCLE
TANK FARM RAW
MATERIAL STORAGE
VCM RECOVERY
VINYL ACETATE
RECOVERY
REACTORS (12) BATCH
POLYMER PROCESS
SLURRY TANKS
CENTRIFUGES
FLASH DRYER
WEIGHING HOPPER
RESIN
HOLDING SILO
I
SCREENING
1
CYCLONE
COMPOUNDING
SALES
RECORD
PRESSING
Figure B-1 • Keysor - Century Corporation Process Flow
-------
B-4
included in the design of an in-plant wastewater pretreatment facility
which is now under study.
Sampling
The company began taking grab samples of air around the PVC plant
work areas after learning of the possible vinyl chloride health prob-
lem. For sampling, a Tedlar bag and a portable 1 liter/min air pump
are mounted on an employee and a 10-min sample of air is collected
while he performs his normal duties. Analyses are performed by an
independent laboratory. The overall range of vinyl chloride concentra-
tions in the work areas has been 3 to 330 ppm, with a 30 ppm average in
most work areas. Concentrations for specific areas are as follows:
Work Area Concentration (PPM)
Recovery Unit 30 Avg.
Drying Systems 30 Avg.
Reactors (during breaking of lines) 330 Max.
Reactors (during PVC unloading) 30 Avg.
Reactors (during VCM charging) 70 Max.
No sampling of the wastewater effluents has been conducted by the
company to date.
-------
APPENDIX C
PERSONS CONTACTED
-------
C-l
Appendix C
PERSONS CONTACTED
B. F. Goodrich Chemical Company, Carson, California
Mr. A. W. Clements, Plant Manager
Mr. W. C. Holbrook, Manager, Environmental Control Engineering
(Corporate Office - Cleveland, Ohio)
Mr. R. Nattkemper, Plant Engineer
American Chemical Corporation, Carson, California
Mr. H. Kling, Plant Manager
Mr. D. A. Grotegut, Plant Engineer
Mr. J. M. Witte, Process Engineer
Mr. G. D. Wina, Process Engineer
Keysor-Century Corporation, Saugus, California
Mr. S. K. Law, Process Engineer
Mr. E. Scott, Chemical Plant Manager
------- |